Epoxidized oil binder compositions and process for preparation of thermoset hardened products

ABSTRACT

In some aspects, the disclosure relates to processes involving a two-component resin system to provide a composite matrix binder. The first component may be a liquid reactive diluent, like an epoxidized vegetable oil, and the second component may be a solid, powdered polymer component, like a carboxylic functional acrylic or polyester, that may react with the liquid component. The liquid component may wet and coat the filler materials, while the powdered resin may soften/melt at higher temperatures below its threshold reactive temperature, thus allowing it to flow, diffuse and mix with the liquid component. This facilities processing and allows use of higher molecular weight resins and/or a higher Tg polymers without solvent use. When used in stone composite formulations with fillers like quartz and/or titanium dioxide, example resulting products have high hardness, very low water absorption, and high mechanical strength along with stain, chemical, and heat resistance.

RELATED APPLICATIONS

The present application is a continuation-in-part of U.S. patentapplication Ser. No. 16/014,781, filed on Jun. 21, 2018, now issued asU.S. Pat. No. 10,513,566, which was a non-provisional application ofU.S. Provisional Application No. 62/523,350, filed Jun. 22, 2017. Thecontent of these applications are incorporated herein by reference intheir entirety for all purposes.

TECHNICAL FIELD

In some aspects, this disclosure relates to compositions including oneor more epoxidized oils or derivatives thereof, such as epoxidizedvegetable oil (e.g. linseed and/or soybean oil), and including one ormore resins having carboxyl or anhydride functionality, such as acrylic,polyester, and/or polybutadiene resins including carboxylic acidfunctional group(s). The compositions may be used in a variety ofapplications, including use and/or incorporation in binder systems (for,e.g. composites), composites, coatings, adhesives, and elastomers.

BACKGROUND

Oil based stone composites using anhydride containing compounds sufferfrom toxicity, discoloration, or hardness issues. For example,methylhexahydrophthalic anhydride is considered a health hazard even atlow levels. Other anhydrides darken the final composite product and maycure non-uniformly due to their solid states.

Example stone composite fabrication processes involve low molecularweight polyester with unsaturated moieties mixed with styrene monomer asa reactive diluent, heated in the presence of suitable catalysts (e.g. afree radical initiator), where the excess unreacted styrene has to beremoved from the system. As another example process, copolymers ofmethyl methacrylate oligomers are used as a binder in the presence of areactive diluent like methyl methacrylate monomer, where the system iscured in the presence of free radicals generating peroxide initiators athigh temperatures to make a hard composite product. In both of theseexamples and other process, the excess unreacted diluent has to beremoved from the system. These reactive diluents are both highly toxicand flammable, and therefore create a hazardous work environment. Asanother example, enclosed and self-contained equipment to properlyhandle vapors from acrylic and styrene monomers is capital intensive inaddition to its toxicity concerns for workers.

Various epoxidized materials are known (e.g. Bisphenol based epoxies),but these have limited environmental resistance and tend to chalk andyellow over time. What's more, the raw materials used to manufacturethese chemicals are environmentally detrimental.

SUMMARY

This Summary provides an introduction to some general concepts relatingto this disclosure in a simplified form, where the general concepts arefurther described below in the Detailed Description. This Summary is notintended to identify key features or essential features of thedisclosure.

In some aspects, the disclosure relates to compositions such ascomposites, adhesives, solvent based coatings and aqueous basedcoatings, powder coatings, and elastomers. Examples of the compositions,e.g., composites, include an epoxy material(s). The epoxy material mayinclude one or more epoxidized oils (and/or derivatives thereof, such asfatty acid derivatives thereof). The epoxy material may have an oxiranepercentage between about 3.0 and about 11.5. The composition may alsoinclude one or more resin materials including carboxylic or anhydridefunctionality. The resin material may have an acid value of about 40 toabout 700. In some examples, the one or more epoxidized oils includevegetable oil(s), such as linseed oil, soybean oil, or a combinationthereof. In certain embodiments, the one or more epoxidized oils arederived from one or more plant-based raw materials.

In certain examples, the resin material(s) comprise an acrylic resin, apolyester resin, or a combination thereof. In various examples, theresin material comprises a carboxylic or anhydride functional acrylic, apolyester with free reactive carboxylic groups, or a combinationthereof. In some examples, the resin material comprises a molecularweight in the range of 500-25,000 Daltons. In certain embodiments theresin material may have a ratio of oxirane to carboxylic groups of about0.9 to about 1.5. The resin material(s) may have a Tg of about 30° C. toabout 90° C. In some examples, the composition is cured using one ormore catalysts. In certain examples, the composition is thermally curedat a temperature of about 50° C. to about 300° C.

In some embodiments, the composition, e.g., composite, further includesone or more fillers, such as quartz granules, marble granules, carbonmaterials such as carbon fibers and/or carbon tubes, glass or glassfibers, silica, ceramic, or a combination thereof. In certain examples,the fillers have a size range of about 0.2-500 μm, or about 10-200 μm.

In some examples, the compositions are powdered compositions, and may becoated onto a substrate and then cured. The powder may have a particlesize of about 10-200 μm. In certain embodiments, the epoxy material(s)and the resin material(s) are dissolved in an organic solvent to form aliquid coating. In some examples, the epoxy material(s) and the resinmaterial(s) are dispersed in water to form an aqueous coatingdispersion. In various embodiments, the dispersion includes astabilizing component, where this component includes one or moreinorganic bases of ammonia, sodium hydroxide, potassium hydroxide, oneor more organic bases of triethylamine, dimethylethanol amine, one ormore Lewis bases, one or more anionic surfactants, one or more nonionicsurfactants, or a combination thereof. In some examples, the compositionis a pigmented or clear liquid coating. In certain embodiments, a liquidcoating composition is applied to one or more metal, wood, glass, and/orplastic substrates. In various examples, the one or more oils and one ormore resin materials are cured into a hard, durable composite. In someembodiments, the composition is applied to one or more substrates ineither liquid or paste form, and the one or more substrates are thenjoined to another substrate, and the joined substrates are heat cured,such that the composition has an adhesive strength sufficient to adherethe substrates together.

In some examples, the one or more epoxidized oils are between about10-70% of the composite, by weight, between about 10-50%, between about15-45%, or between about 35%-45%, but other weights and ratios may beused. In certain embodiments, the composition includes an epoxy materialcombined with an anhydride or carboxyl functional polybutadiene having amolecular weight of 500 to 10,000 Daltons.

In certain embodiments, the composite has a Barcol Hardness of about 70BU-80 BU. In some examples, the composite has a Barcol Hardness of about70 BU or more, about 75 or more, or about 80 BU or more. In certainexamples, the composites have a density of about 2.00 g/cm³ or more,about 2.10 or more, about 2.15 or more, about 2.20 or more, about 2.25or more, about 2.30 or more, about 2.35 or more, or about 2.40 or more.

In various embodiments, the composite also includes one or more UVstabilizers, one or more thixotropic binders, or a combination thereof.In certain examples, the epoxy material is derivatized by partiallyreacting the oxirane functionality with poly carboxyl functionaloligomers, polyacid compounds, or a combination thereof. In someembodiments, the epoxy material is partially or fully acrylated, thecomposition includes a liquid poly unsaturated multifunctional acrylateor vinylic compound, and the composition is cured by a thermallyinitiated curing process using a peroxide initiator.

In some examples, one or more processing aids are used in theformulation of the composition, where, the one or more processing aidsmay include one or more solvents. In various examples, the compositionsare solvent-free. In some embodiments, the amount of bio-renewablecontent of the composition is 20% or more, by weight. In variousexamples, when the composition is applied to one or more substrates, ithas an adhesive strength sufficient to maintain adhesion to the one ormore substrates when exposed to forces up to 1750 psi, or more. In someexamples, the composition comprises an amount of amino resins that isless than or equal to the epoxy equivalent levels. In certain examples,the composition includes a polyisocyanate material, a blockedpolyisocyanate material, an isocyanate blocked prepolymer material, anisocyanate terminated prepolymer material, or a combination thereof.

In some examples, the composition has a flexural strength of 7000 psi ormore. In various embodiments, the composition has a twenty-four hourwater absorption rate of 0.03% or less. In various embodiments, thecomposition has a seven day water absorption rate of 0.1% or less. Insome examples, the composite has a flexural strength of 7000 psi or moreand a Barcol Hardness of 70 BU or more. In various embodiments, thecomposition has a chemical resistance such that there is no effect in amarker resistance test. In certain embodiments, the composition has achemical resistance such that there is no effect after 16 hours ofexposure to a 10% caustic solution.

In accordance with another aspect of the disclosure, processes aredisclosed. In some examples, the process includes combining and heatingan epoxy material and a resin material, for example above the glasstransition temperature of the resin material and curing the mixture. Theepoxy material may include one or more epoxidized vegetable oils, one ormore epoxidized vegetable oil derivatives, or a combination thereof. Theepoxy material may have an oxirane percentage between about 3.0 andabout 11.5. In some examples, the resin material includes carboxylic oranhydride functionality. In some examples, the resin material has anacid value in a range of 40-700. In certain examples, the resin materialincludes an acrylic resin, a polyester resin, or a combination thereof,or may include one or more acrylic resins, one or more polyester resins,or a combination thereof. In some examples, the resin material mayinclude other materials. In various embodiments, the resin materialincludes carboxylic or anhydride functional acrylic, a polyester withfree reactive carboxylic groups, or a combination thereof. In certainexamples of the processes, one or more fillers are mixed with the epoxymaterial and the resin material.

In certain examples, the process includes heating one or more epoxidizedoils and one or more resin materials including carboxylic functionalityabove the glass transition temperature of the one or more resinmaterials, and mixing the heated one or more oils and one or morematerials to form a mixture. Then, the mixture may then be cured to forma composite. In certain examples, one or more fillers are also heatedand mixed with the one or more oils and one or more materials, or addedto a formed mixture. In various embodiments, one or more solvents arealso heated and mixed with the one or more oils and one or morematerials.

In certain aspects, the disclosure related to processes involving a twocomponent resin system to function as a composite matrix binder. Thefirst component may be a liquid reactive diluent, for example anepoxidized vegetable oil, and the second component may be a solidpolymer component (or a compound) in form of a powder, for example acarboxylic functional acrylic or polyester that is capable of reactingwith the liquid component, e.g. at higher temperatures. The liquidcomponent may be capable of wetting and coating fillers materials. Thepowdered resin may be capable of softening and/or melting and flowing athigher temperatures that are still below its threshold reactivetemperature, thus allowing it to flow, diffuse and/or mix with theliquid component upon softening and/or melting. This approach allowsease and possibility of using a higher molecular weight resin and or ahigher Tg polymer in the formulation without the use of a solvent. Whenused in stone composite formulations with suitable fillers like quartzand titanium dioxide, example products have high hardness, very lowwater absorption, and high mechanical strength along with stain,chemical, and heat resistance.

These summary descriptions merely provide examples of materials,compositions, systems, composites, processes and/or process steps thatmay be performed in one or more embodiments. In certain embodiments,materials and methods include additional combinations or substitutions.To that end, other details and features will be described in thesections that follow. Any of the features discussed in the embodimentsof one aspect may be features of embodiments of any other aspectdiscussed herein. Moreover, additional and alternative suitablevariations, features, aspects and steps will be recognized by thoseskilled in the art given the benefit of this disclosure.

These and other features, advantages, and objects of the presentdisclosure will be further understood and appreciated by those skilledin the art by reference to the following specification.

DETAILED DESCRIPTION

The examples, materials and methods of described herein provide, interalia, materials, compositions, composites, and/or binder systems, andprocesses of making the same. These and other aspects, features andadvantages of the disclosure or of certain embodiments of the disclosurewill be further understood by those skilled in the art from thefollowing description of example embodiments. It is to be understoodthat other modifications may be made from the specifically describedmethods and systems without departing from the scope of the presentdisclosure. It is also to be understood that the specific materials,systems, and described in the following specification, are simplyexample embodiments. Hence, specific amounts and other physicalcharacteristics relating to the embodiments disclosed herein are not tobe considered as limiting.

In some aspects, the disclosure relates to composites or systemsutilizing one or more composites. For example, in certain applications,a thermoset epoxy-based binder system is provided for stone compositeapplications (but other applications such as coatings or adhesives arepossible, as described below, where in some example applications thethermoset material is not set until one or more substrates are coated,joined together, or other pre-setting actions are completed, and in someexamples are non-binder systems). In some examples, a composite includesan epoxy material that includes one or more epoxidized oils and one ormore resin materials that include carboxylic and/or anhydridefunctionality. In certain examples, other materials, such as coatings,include the one or more epoxidized oils and one or more resin materialsincluding, e.g., carboxylic functionality.

In certain examples, the one or more epoxidized oils are derived fromone or more plant based raw materials. The oils may include one or moreof linseed oil, soybean oil, or another vegetable oil (e.g. sunfloweroil, safflower oil, or others). Other example oils may include one ormore of olive oil, sesame oil, sunflower seed oil, corn germ oil, palmoil, and rapeseed oil. The epoxidized oils may include or consist of aderivative of any of the above example oils (such as an esterderivative), or other suitable oils such as plant-based oils. Whilecertain specific examples of this disclosure recite particular type ofoil, such as linseed, soybean or may simply refer to a vegetable oil,other oils maybe be substituted for this specifically recited oil toprovide other example compositions of this disclosure, or may becombined with the recited oil(s). In some examples, a variety avegetable oils are used together (e.g. soybean and linseed). Theepoxidized oils of this disclosure (or their derivatives) may benon-toxic, nonvolatile reactive liquids made from sustainableplant-based raw materials, and therefore provide several advantages inthe production, acquisition, refining, and/or use of the materials usedin the composition.

The epoxidized oil(s) may be non-volatile and/or nonionic. The oils maycontain compounds having C5-C26 aliphatic chains (but may also containcarbon chain(s) of other length), which may have linear and/or branchedaliphatic groups. In some examples, the oxirane/epoxide oxygen contentis about 3% or more (by weight) of the oil(s). In some examples, it isabout 5% or more, 7% or more, about 9% or more, about 11% or more, about13% or more, or about 15% or more. In some examples, the oxirane/epoxidecontent is about 2.0-14% by weight, about 3.0-11.5% by weight, about5-10% by weight, about 6.5-9.5%, about 6.5-7.5%, about 7.0-7.5%, about8.5-9.5%, or about 9.0-9.5%. This can provide a high reactivity of theoil through the number of oxirane/epoxide functionality sites on the oilmolecules. As a specific example, an epoxidized linseed oil withrelatively high oxirane content (e.g., about 9% minimum) containsapproximately 5 epoxide reaction sites and 3 ester sites per molecule,and averages about 5.5 epoxide groups per epoxidized molecule. Thus,each oil molecule in this example is capable of reacting with an averageof five and a half equivalents of an acid, such as a carboxylic acid. Asanother specific example, use of epoxidized soybean oil with oxiranecontent of about 7% or more provides an average of 4.5 reactive groupsper molecule. Oils with a higher degree of epoxidation may yield aharder product, that will require relatively smaller amounts of oil,because the epoxidized oil has a relatively higher degree offunctionality. As one example, a High IV Epoxidized Linseed Oil with anoxirane content of about 10.7 or greater may be used; this yields aharder product that requires less ELO because it has higherfunctionality. In some examples, the epoxy material is derivatized bypartially reacting the oxirane functionality with poly carboxylfunctional oligomers, polyacid compounds, or a combination thereof. Insome examples, the epoxy material is partially or fully acrylated. Invarious examples, the composition also includes a liquid polyunsaturated multifunctional acrylate or vinylic compound.

In some examples, the epoxidized oils have a molecular weight rangingfrom about 100-30,000 Daltons, about 100-20,000 Daltons, about500-25,000 Daltons, about 5,000-15,000 Daltons, about 7,000-13,000Daltons, or about 9,000-11,000 Daltons. In some examples, thecomposition also include an anhydride or carboxyl functionalpolybutadiene having a molecular weight of 500 to 10,000 Daltons, or1,000 to 5,000 Daltons, for example in combination with an epoxymaterial. In various examples the resin materials have a molecularweight of about 200 Daltons or more, about 500 Daltons or more, about1,000 Daltons or more, about 5,000 Daltons or more, about 12,000 Daltonsor more, or about 20,000 Daltons or more. In certain examples, the resinmaterials have a molecular weight of about 15,000 Daltons or less, about5,000 Daltons or less, about 1,000 Daltons or less, or about 500 Daltonsor less.

In various examples, the one or more resin materials include one or moreof an acrylic resin, a polyester resin, a polyurethane resin or acombination thereof. In at least the composite and/or binder systemapplications of the present disclosure, the resin or resins should becurable compounds compatible with the epoxidized oil. The resin(s) mayhave a high glass transition temperature (Tg). In some examples, thematerials have a Tg of about 25 degrees Celsius or more, about 30degrees Celsius or more, about 50 degrees Celsius or more, about 60degrees Celsius or more, or about 70 degrees Celsius or more. In variousexamples, the one or more resin materials have a Tg between about 20-100degrees Celsius, about 30-90 degrees Celsius, 40-80 degrees Celsius,about 50-70 degrees Celsius, about 50-60 degrees Celsius, or about50-100 degrees Celsius. The resin may initially be present as a solid,e.g. as powdered, flakes, granules, or a combination thereof. In someexamples, the resin is or includes a carboxylic or anhydride functionalacrylic. In some examples, the resin is or includes a polyester withfree reactive carboxylic groups. The epoxy and resin material(s) mayhave ratio of oxirane to carboxylic groups of about 0.9-1.5. In otherexamples, the ratio is about 0.5-2.0. In some examples, the ratio isabout 0.5 or more, about 0.9 or more, about 1.1 or more, about 1.3 ormore, about 1.5 or more, about 1.7 or more, or about 1.9 or more.

In some examples, such as those for binder compositions for a compositeor a liquid coating, an epoxidized oil or oils (such as epoxidizedvegetable oil or its derivatives) react with one or more resins and/ormolecules having carboxylic or hydroxyl functionality, or both. Thereaction of the epoxy group with the acid can generate a hydroxyl group,while the hydroxyl group can react with the epoxy group to generateether linkages. Alternatively, the epoxy group may react with methylolgroups, melamine resins, and/or isocyanate groups. Examples of carboxylfunctional resins with a high amount of reactable free acid or acidgenerating groups include a polyacrylate, polyester orcarboxyl-terminated butadiene-acrylonitrile (CTBN) resin. Acidgenerating anhydride based systems can also be used, e.g. maleicanhydride grafted polybutadiene. There may also be a small amount ofreactive diluent that can be a derivative of the epoxidized oil, e.g.epoxidized methyl linseedate.

In some examples, one or more polyacrylic resins are used for, e.g. abinder composition or other application. The polyacrylic resin (orresins) may include copolymers of carboxylic group containing moietiesthat can react with epoxy groups, such as meth(acrylic acid), and/orhydroxyl groups like hydroxyl ethyl meth(acrylate). In some examples,the polyacrylic resin (or resins) may include monomers, such as methylmethacrylate, glycidyl methacrylate, and/or even vinyl based monomers,like styrene, to increase Tg and improve hardness. In certainembodiments, the polyacrylic resin (or resins) may include butyl meth(acrylate) to improve flexibility and/or compatibility. In someexamples, an acrylate resin material may include glycidyl methacrylatebased acrylates, where the carboxylic acrylate material may react withthe epoxidized oil (e.g. an ELO materials) as well as the glycidylmethacrylate acrylate. The acrylic resin material may be entirely absentof any pendant hydroxyl groups in the backbone, or hydroxyl groups mayonly be present in an amount of about 5% or less, about 2% or less,about 1% or less, or about 0.5% or less, of the monomers forming thepolymer of the acrylic resin material. The acrylic resin material may beentirely absent of any aromatic groups in the backbone, or aromaticgroups may only be present in an amount of about 5% or less, about 2% orless, about 1% or less, or about 0.5% or less, of the monomers formingthe polymer of the acrylic resin material. In some examples, the acidfunctionality of the resin is derived from olfenically unsaturated acidfunctional monomers with pendant carboxylic groups.

In some examples, a polyester resin is used for e.g. a bindercomposition or other application. The binder composition may be suitablefor a composite matrix application, a coating application, or foradhering substrates. In certain examples, compositions may include oneor more polyester resins with excess carboxylic groups, where these mayresult from the reaction between poly carboxylic acid and poly hydroxylmolecules with a molar excess of the poly acids, in the presence of asuitable catalyst. There are numerous polyacids suitable or theseembodiments, including but not limited to cyclohexane dicarboxylic acid,adipic acid, citric acid, succinic acid maleic acid, lactic acid,sebacic acid, aromatic polyacids such as but not limited to isophthalicacid, terephthalic acid, phthalic acid, and/or one or more anhydridessuch as but not limited to trimellitic anhydride and/or phthalicanhydride. In certain examples, polyols may be used to react with thepolyacid(s) to generate the ester linkages, such as neopentyl glycol,1,4 butane diol, 1,6 hexane diol, trimethylolpropane, and/ortrimethylolethane. In some examples, the free reactive carboxylic groupsin the polyester resin are formed in a condensation reaction usingexcess difunctional and/or trifunctional polyacid compounds. In certainexamples, the polyester component is made in a single step synthesis. Insome examples, there are no polyester resins that are hydroxylterminated present in the compositions.

Using, for example, an acrylic resin and/or a polyester resin in powderform along with an epoxidized oil or oils, such as epoxidized linseedoil, as the liquid plasticizer helps suspend the resin in the oil andlower the operational viscosity of the resin system. This may facilitatemixing, dispersion, and ultimately the formation of, e.g. a curedcomposite material. In some examples, the one or more epoxidized oilsare between about 10-70% of the composite (or, in other embodiments,other compositions such as coatings), by weight, between about 10-50%,between about 15-45%, or between about 35%-45%.

The resin material(s) may include oligomeric resins. In some examples,the amount of amino resins is less than or equal to the epoxy equivalentlevels. In some examples, the composition includes a polyisocyanatematerial, a blocked polyisocyanate material, an isocyanate blockedprepolymer material, an isocyanate terminated prepolymer material, or acombination of the same and/or multiple materials in these categories.

In some examples, the resin materials have a molecular weight rangingfrom about 600-15,000 Daltons, about 1,000-20,000 Daltons, about1,500-11,000 Daltons, or about 5,000-15,000 Daltons. In various examplesthe resin materials have a molecular weight of about 1500 Daltons ormore, about 4,000 Daltons or more, about 10,000 Daltons or more, orabout 15,000 Daltons or more. In certain examples the resin materialshave a molecular weight of about 15,000 Daltons or less, about 10,000Daltons or less, about 5,000 Daltons or less, or about 2,000 Daltons orless. Aqueous based systems may use materials reaching 25,000 to 50,000Daltons, or even greater values. In case of water based applications themolecular weight of the carboxyl functional latex can be 50,000 Daltonsor more, 75.000 or more, or 100,000 or more.

In certain composition examples, the one or more epoxidized oils arebetween about 10-70%, by weight, of the total combined weight of theepoxidized oil(s) and the resin material(s), between about 10-50%,between about 15-45%, between about 35-45%, or between about 40-80%. Insome examples, the epoxidized oil(s) (and/or derivatives) are 10% byweight or more, 20% or more, 30% or more, 40% or more, 50% or more, 60%or more or 70% or more. These weight ranges or values of oil(s) (orderivatives) may also be used based on the entire composition weight,for example, in a composition including oil(s), resin material(s), andone or more additives, such as a filler. In certain examples, thus, theone or more epoxidized oils are between about 10-70%, by weight, of theentire composition weight. In various embodiments, the one or moreepoxidized oils are between about 15-60%, by weight, of the entirecomposition weight, about 20-25% by weight, about 10-25% by weight,about 30-50% by weight, or about 20-45% by weight. In certaincomposition embodiments, the resin material(s) are the only otheringredients, while in others one or more additional ingredients arepresent.

In some embodiments, the resin material, such as a polyester or acrylicresin, includes carboxylic functionality. The epoxide group in theoil(s) may then react with the carboxylic acid functionality to formneutral compounds, i.e. the epoxide ring opens in the presence of thecarboxylic acid group to form neutral esters of the acid present. Incertain composition examples, the one or more resin materials arebetween about 20-90%, by weight, of the total combined weight of theepoxidized oil(s) and the resin material(s), between about 20-60%,between about 35-55%, between about 40-50%, between about 45-60%, orbetween about 20-35%. In some examples, the resin materials(s) are 50%by weight or more, 10% or more, 20% or more, 30% or more, 40% or more,50% or more, 60% or more or 70% or more. In certain compositionembodiments, the resin material(s) are the only other ingredients, whilein others one or more additional ingredients are present. These weightranges or values of resins materials may also be used based on theentire composition weight, for example, in a composition includingoil(s), resin material(s), and one or more additives, such as a filleror fillers. In certain examples, thus, the one or more resin materialsare between about 20-60%, by weight, of the entire composition weight.In various embodiments, the one or more epoxidized oils are betweenabout 20-30%, by weight, of the entire composition weight, about 45-60%by weight, about 35-50%, or about 20-35% by weight.

In some embodiments, the composite further includes one or more fillersand/or additives, such as quartz, marble, or a combination thereof. Thefillers may be granules appropriately sized for the application anddesired properties. In some examples, the fillers and/or additivesinclude one or more of mineral fillers, metal fillers (and/or metallicalloy fillers), granite fillers, ceramic fillers, various fibersincluding carbon fibers, carbon nanotubes, one or more conductivematerials, and/or decorative elements such as pigments,pigmented/colored materials, dyes, or decorative elements such as metalflakes. In some examples, the fillers may be or include one or moreinorganic fillers, such as alumina trihydrate, calcium carbonate,titanium dioxide, or other compounds including one or more alkalimetals, alkali earth metals, or transition metals. Various ligands maybe coordinated with an appropriate filler metal material. In certainexamples, the fillers have a size range of about 0.2-500 μm, about100-500 μm, about 1-10 μm, about 1-100 μm, about 100-500 μm, about100-1000 μm, about 0.1-0.5 μm, about 0.1-0.2 μm, about 0.2-1 μm or about0.2-0.5 μm. In some examples, the one or more fillers may be present inan amount of about 30% or more by weight of the entire composition. Incertain examples, the one or more fillers may be about 50% or more byweight of the entire composition, about 60% or more, about 70% or more,about 80% or more, about 90% or more, or about 95% or more. In variousembodiments, the weight ratio of a binder (including epoxidized oil(s)and resin(s) material) to one or more fillers is about 1:3 or more,about 1:5 or more, about 1:8 or more, about 1:9 or more, or about 1:10or more.

In various examples, the one or more oils and one or more resinmaterials are cured into a hard, durable composite. Example compositionsmay include acrylic and/or polyester resins with carboxylicfunctionality and having high glass transition temperature (Tg) that areblended with one or more epoxidized oils, such as linseed or vegetableoil and/or their derivatives, in suitable molar ratios along withfillers such as quartz to make composites. These and other composites(e.g. those without fillers) may have high Barcol Hardness, impactresistance, and/or chemical, water and UV resistance. The cured materialand/or binder may have high gloss as well as clarity. Cure temperaturesmay be from 50° C. to about 300° C., and various cure times andconditions may be used depending on the characteristics of thecomposition and desired cure characteristics. Prior to curing, thecomposition may be mixed, intermittingly or continuously, for examplefor one hour. In some examples, the mixtures are allowed to sit prior tocuring after mixing. Compositions may be partially or completely driedprior to curing.

In some examples, the composition is heated above the Tg of thecarboxylic functional resin along with an epoxidized linseed oil(“ELO”). The ELO and/or other epoxidized oil (or derivative) may act asa reactive, nonvolatile diluent to assist in uniformly wetting theparticle surface and compaction of any binder filler (such as quartzgranules of size range of 0.2-500 μm). After the composition isuniformly mixed and settled, the temperature may be raised to about 140°C. or more (or other appropriate temperature) to cure the oil(s) withthe carboxylic functionality resin to form a hard durable chemically andthermally resistant composite. The relatively high functionality of theepoxidized oils may result in a harder cured product by allowing thestoichiometry to balance such that relatively lower amounts of oil areneeded. The final product may have a non-hazy appearance, non-yellowedand/or non-colored appearance (unless desired and achieved throughintentional colorants such as added filler materials), and theconstitute components may be stable and cure relatively quickly atelevated temperatures. Moreover, the product may not discolor (e.g. notyellow) even after long exposure to sunlight/UV light, e.g. one month ormore, two months or more, three months or more, or four months or more,or six months or more, or one year or more, or five years or more, orten years or more, or fifteen years or more. In some examples, thecompositions do not use any unsaturated ricinoleic acid or similarcompounds which have a tendency to yellow or only have such componentsin very small amounts, e.g. about 5% or less, about 2% or less, about 1%or less, about 0.5% or less, or about 0.25% or less, by weight of thecomposition.

There are also noteworthy benefits in stability because the mechanism ofreaction is through epoxy ring opening by potent carboxylic groups atelevated temperatures, whether in the presence or absence of suitablecatalyst. In some examples, pendant, free carboxylic groups thatintentionally have very low reactivity at lower temperatures (e.g. 120degrees Celsius or less, unless coupled with a catalyst) towardsinternal epoxy groups are used. This may allow more control insubsequent processing, e.g. longer processing and working time forcompacting, softening and/or melting the materials, such as a powderedresin, removal of air from the mold, etc., whereas higher reactivitycould result in premature gelling, frustrating the processing. Thisreaction framework also allows one to achieve a more controlled, andtherefore a more uniform, cure. For example, in coatings applications,this allows melt, flow, levelling as the temperature is ramped up topeak temperature, especially in applications like coil coatings Thus,the compositions may provide practical compositional pot life and shelfstability at room temperature, and may have a pot life on the scale ofmonths (e.g. remain stable and usable for about one month or more, abouttwo months or more, about three months or more, or about six months ormore), but still result in high performance materials when cured. Forexample, the components may be stored together as a one pot system forlong periods, on the order of at least months, and then selectivelyreacted when cured at elevated temperatures (e.g. about 140 degreesCelsius or more, or about 150 degrees or more), as these elevatedtemperatures are needed to cause the reaction between the components andprovide a fully cured product. Use of relatively higher Tg resins (e.g.above about 30° C., or above about 50 degrees ° C.) may further ensurestorage ability and avoid premature reaction, separation during storageor initial processing. The material performance properties canoptionally be enhanced by blending the epoxy and resin materials withhydroxyl group reacting secondary crosslinkers, like one or more aminoresins, to react with the hydroxyl groups generated from the oxiranering opening in-situ.

There are a number of advantages that result from the use of epoxidizedoils. For example, ELO and other epoxidized oils of this disclosure havebuilt in aliphatic chains resulting in a composite with excellent impactresistance, as opposed to conventional Bisphenol A type epoxies thatinherently tend to have poor impact resistance due to the presence ofaromatic groups (and thus often had to be formulated with aliphaticcompounds to improve these properties). Additionally, the reaction ofthe oxirane groups with carboxylic groups generates hydroxyl groupsgiving excellent adhesion to polar surfaces and fillers. Meanwhile, thelong aliphatic moieties give excellent water resistance as well asresistance to polar solvents (for example, example compositions havehigh solvent resistance, e.g. 200+ MEK double rubs with almost noburnish with polar or nonpolar solvents, and are also resistant toisopropyl alcohol and xylene, as illustrated below). Finally, the highpercentage of oxirane groups gives a dense cured network withoutcompromising toughness. The virtual absence of unsaturation in, e.g.,ELO also provides a way to formulate non-yellowing compositions. Itsincorporation gives strong adhesion due to the opening of the oxiranering, good hydrophobicity, as well as chemical and stain resistance.Other appropriate oils or derivatives can similarly provide some or allof these benefits, as illustrated herein. In particular, the level ofhardness, degree of curing, and overall compatibility of the epoxidizedoils with the various resins was surprising and unexpected. It wasunexpectedly determined that ELO, for example, cures with certain acidswith relatively short gel times (e.g. <15 min) at elevated temperatures(e.g. 145 degrees Celsius), and had desirable chemical properties. Incertain examples, the oil(s) and resin(s) materials may have gel timesof about 30 minutes or less, about 20 minutes or less, about 15 minutesor less, or about 10 minutes or less.

As an example, compositions utilizing the epoxidized oils and resins mayhave high Barcol Hardness and impact resistance, along with chemical,water and ultraviolet resistance. The exterior resistance can be furtherenhanced by formulating with additives, such as hindered amines (HALS)and/or UV stabilizers. Example compositions may also be used for coatingand structural adhesive applications, for example as an alternative toBisphenol A based epoxies or in formaldehyde free coating applicationsas a replacement for amino curing agents.

Therefore, the present disclosure provides high performance, non-toxicexample products that are also beneficially made from sustainable rawmaterials. This can be advantageous to the ultimate users of theproducts, e.g., by facilitating the acquisition of LEED (Leadership inEnergy and Environmental Design) certifications, which are highlydesirable in commercial and residential construction. In certainexamples, the compositions use non-toxic components, for example arefree of styrene monomer, anhydride monomer, and butyl acrylate monomer,and contain no petrochemical based diallyl phthalate, which arepreviously relied on in the industry but all have major health concernsbecause of their toxicity, or only have such monomers in very smallamounts, e.g. about 5% or less, about 2% or less, about 1% or less,about 0.5% or less, or about 0.25% or less, by weight, of the resinmaterial. Similar, example processes of the disclosure do not utilizeany of these materials as diluents in the processing and creation (whichcan result in unreacted volatile monomers necessitating removal orremaining in the products). Instead, the example compositions andprocesses deliver a non-toxic product and eliminate worker exposure to ahazardous environment. Moreover, these provide bio-based highperformance compositions with desirable properties, but withoutpresenting risks or relying on large amounts of petrochemical basedmaterials. Furthermore, example processes and compositions do not usephenolics to obtain performance, e.g. because they instead utilizerelatively higher Tg acrylics.

In certain embodiments, the composite has a Barcol Hardness of about 70BU-80 BU, in others about 65-70, in others about 70-75, in others about75-80, and in others about 80-85. In some examples, a composite has aBarcol Hardness of about 60 BU or more, about 70 BU or more, or about 80BU or more. In various embodiments, the composite also includes one ormore UV stabilizers, one or more thixotropic binders (i.e. materialsthat become less viscous under applied stress), or a combinationthereof. In certain examples, the materials and/or composites mayutilize or incorporate one or more processing aids. In some examples,the one or more processing aids include one or more solvents.

In accordance with another aspect of the disclosure, processes aredisclosed. In some examples, the process includes heating one or moreepoxidized oils and one or more resin materials including carboxylicfunctionality, and mixing the heated one or more oils and one or morematerials to form a mixture. In some examples, the materials are heatedabove the glass transition temperature of the one or more resinmaterials with carboxyl functionality, where the epoxidized oil(s) (suchas epoxidized linseed oil), acts as a reactive nonvolatile diluent. Incertain examples, one or more fillers are also heated and mixed with theone or more oils and one or more materials. When the oil(s) act as areactive nonvolatile diluent, this can assist in uniformly mixing andcompacting and bind any fillers that are added (such as, but not limitedto, quartz granules, e.g. having a size range of about 0.1-500micrometers). Then, in some examples, the mixture is cured to form acomposite. For example, the composition may be uniformly mixed andsettled and then the temperature is raised to 140 degrees C. to curethe, e.g., epoxidized linseed oil (or other cure temperatures asappropriate based on the oil(s) used) with the carboxylic functionalityof the resin to form a hard durable chemically and thermally resistantcomposite. Thus, the epoxidized oils (such as ELO) and their derivativesmay be used in, e.g., powder resin applications, or at higher levels asepoxy blends for chip and impact resistant exterior or interior heatcured coating applications. In various embodiments, one or more solventsare also heated and mixed with the one or more oils and one or morematerials, and optionally any fillers, or the fillers may besubsequently added.

In some embodiments, the composite is an extrudable material. Forexample, the composite materials may be mixed at a relatively lowtemperature (e.g. under 140 degrees Celsius, but a high enoughtemperature to facilitate mixing as needed based on the materialsutilized) and mechanically shaped by, e.g., one or more rollers, thenextruded (or molded) through one or more dies, molds, casts, and so on.In some examples, the mixed materials are directly extruded without the,e.g. rollers. The extrusion may be intermittent or continuous. Afterextrusion, the materials may be cured at an elevated temperature (e.g.above 140 degrees Celsius). A variety of composite shapes, such assheets of material, may be cured in this manner. These sheets or othershapes may be used in a variety of applications, such as countertops orother structural materials. In some examples, the composite (e.g. acured sheet) may be further mechanically manipulated under heating tofacilitate application, installation, and the like, for example, to foldor reform the profile of the e.g. sheet.

In some examples, the composition is a powder. The powder may have asize of about 10-200 μm. In some examples, the powder size is about 10μm or more, about 25 μm or more, about 50 μm or more, about 100 μm ormore, about 150 μm or more, or about 200 μm or more. The poweredcomposition may be coated onto a substrate or substrates and is thencured, for example as a powder coating application.

In certain examples, the compositions, such as a composite, have a lowwater absorption rate. In certain examples, the composition, e.g.composite, has a water absorption of 0.03% or less over 24 hours, 0.02or less, or 0.05% or less. In other examples, the water absorption is0.2% or less over 24 hours, 0.5% or less, 0.75% or less, 1.0% or less,or 1.5% or less. It is noted that some relatively higher level testingresults may be present due to testing equipment limitations. In exampletesting conditions with more optimized formulations and/or testingequipment, the water absorption may be much lower (or other proprietiesmay have different, more optimized results). In some examples, thecomposition, e.g. a composite, has a water absorption of 0.1% or lessover 7 days, 0.05% or less, 0.15% or less, or 0.2% or less.

When utilized as an adhesive, as illustrated below, example compositionsmay have sufficient mechanical strength such that the compositionsmaintain structural integrity when exposed to a force of 1000 psi ormore, 1200 psi or more, 1500 psi or more, 1750 psi or more, or 2000 psior more. In some examples, the adhesive strength is greater than thecomposite strength (in terms of ability to withstand forces). In variousembodiments, the example compositions may have sufficient mechanicalstrength such that the compositions maintain structural integrity whenexposed to a forces up to 1000 1200 psi, 1500 psi, 1750 psi, or 2000psi.

The cured compositions may have a number of desirable properties asdescribed herein. In some examples, the compositions have an adhesionvalue of 5 A on steel as measured by ASTM D3359. In certain examples,the compositions have an adhesion value of 5 A on phosphated steel asmeasured by ASTM D3359. In various embodiments, the compositions have anadhesion value of 4-5 A on aluminum as measured by ASTM D3359. Incertain examples, the compositions have a hardness value of >6H or 6H asmeasured by ASTM3363 (on steel). In various examples, the compositionshave a MEK Resistance value of about 100 as measured by ASTM 4752 (onsteel). In other examples, the compositions have MEK resistance of 150or more, 175 or more, or 200 or more, as measured by ASTM 4752 (onsteel).

In some embodiments, the compositions have a gloss value of about 90(twenty degree angle), about 94 (sixty degree angle), and/or about 98(85 degree angle) as measured by ASTM D523 (on aluminum). In certainembodiments, the compositions have a gloss value of about 82 (twentydegrees) about 94 (sixty degrees), and/or about 98 (85 degrees) asmeasured by ASTM D523 (on aluminum). In various examples, embodiments,the compositions have a gloss value of about 80 or more (twentydegrees), about 90 or more (sixty degrees), and/or about 95 or more (85degrees) as measured by ASTM D523 (on aluminum). In certain examples,embodiments, the compositions have a gloss value of about 90 or more(twenty degrees), about 94 or more (sixty degrees), and/or about 98 ormore (85 degrees) as measured by ASTM D523 (on aluminum). In variousembodiments, the compositions have a chemical resistance value of 5 asmeasured by ASTM D1308 using 10% sulfuric acid and a steel substrate. Incertain embodiments, the compositions have a chemical resistance valueof 5 as measured by ASTM D1308 using xylene and a steel substrate. Insome examples, the compositions have a chemical resistance value of 5 asmeasured by ASTM D1308 using isopropyl alcohol and a steel substrate. Invarious embodiments, the compositions have a chemical resistance valueof 5 as measured by ASTM D1308 using water and a steel substrate.

In some embodiments, the compositions pass with a ⅛″ value theflexibility by conical mandrel bend testing by ASTM D522 on steel. Invarious embodiments, the compositions fail at a 6 T value theflexibility by t-bend testing by ASTM D4145 on steel. In some examples,the compositions have an impact resistance such that they pass 60 ormore direct impacts as tested by ASTM D2794 (on steel), or 70 or moredirect impacts. In certain embodiments, the compositions have an impactresistance such that they pass 50 or more reverse impacts as tested byASTM D2794 (on steel), 60 or more reverse impacts, or 70 or more reverseimpacts. Example samples having one or more of the above properties mayhave a thickness of about 1.0 mils, about 1.1 mils, about 1.2 mils,about 1.3 mils, or about 1.0-1.3 mils.

In some examples, the cured composites have a resistance to sodiumhydroxide such that there is no effect after 24 hours of exposure to 10%NaOH or 2.5 N NaOH. In various examples, there is no effect from amarker stain. In some examples, there is no effect on a film after 24hours of exposure to 2% H₂SO₄.

The compositions may be non-hazardous. In some examples, thecompositions are solvent-free, such as solvent-free composites. In someexamples, the compositions have a high degree of bio-renewable content,such as composite with a high degree of bio-renewable content.

EXAMPLE FORMULATIONS, APPLICATIONS AND SYSTEMS

The applications of the oil and resin compositions are numerous, butthere may be particular advantages for binder systems, composites suchas stone composites, coatings such as powder coatings or liquidcoatings, as well as adhesive and/or elastomer applications. Thecompositions may include one or more fillers such as quartz and/ormarble. ELO, for example, along with polymer resins having pendantcarboxylic functional groups, for example, may be used as a bindermatrix for other composite applications using glass, wood, carbon, orother fibers, fillers and/or additives, both natural and synthetic,including, e.g. conducive materials, carbon nanotubes, and/or carbonfibers. In some examples, the compositions provide liquid coatings thatmay be applied to one or more metal, wood, glass, or plastic substrates.Such coatings may, for example, have utility in industrial, automotive,appliance coating applications, fiberglass sizing applications,composite laminate applications or other applications, for examplethrough the coating of components, sheets, or coils.

The use of EVO, ESO, ELO, or other natural, plant-based epoxidized oilsin the composite resin matrix can offer several advantages includingsuperior hydrolytic stability compared to polyester. Varying the Tg andmolar proportions of the resin, e.g. an acrylic and/or polyester resin,it is possible to increase the hardness of the composite. Therefore, insome aspects, the compositions are durable, have beneficial mechanicalproperties (such as Barcol Hardness of 70 BU or more), and/or chemicallyresistant surfaces. Through appropriate combinations, the resin(s) mayimpart desirable characteristics such as hardness, clarity, and/or lowcolor with exterior durability towards UV light and other elements,while the epoxy component(s) may impart desirable characteristics suchflexibility/impact properties, improved adhesion, chemical and waterresistance, and/or alkali resistance.

To form examples of the compositions of this disclosure, in someembodiments, a mixture of at least one oil and at least one resinmaterial is heated above the Tg of the carboxylic functional resin,where the ELO (and/or other oils(s)) may act as a reactive nonvolatilediluent to assist in uniformly compacting and binding fillers, such asquartz fillers. The liquid plasticizer may help suspend the resin in ELOand lower the operational viscosity of the resin system. The resinsoftened by ELO may then be used to wet the quartz filler (or otherfiller(s)) to make a paste-like composition. The process may be assistedby the addition of one or more solvents, such as non-HAPS volatilesolvent. The mixture can be dried by removal of the solvent. The dryformulated mixture can conveniently transported, if desired, to variousfabrication locations for curing and fabricating the finished product.This mixture may, after being thoroughly blended, be added into a heatedmold cavity and progressively compressed, or compressed viavibro-compression vacuum process, during filling and melting. Theproduct may then be compressed in the mold and cured, for example at150° C. for 60 to 90 minutes, but other temperatures and time ranges maybe appropriate based on the materials used, size of the product, andother factors. The optional use of a suitable catalyst (or catalysts)may further lower the cure time and/or temperatures needed. Examplecatalysts include nitrogen containing catalysts such imidazoles, forexample 1-methyl imidazole, or derivatives of toluene sulfonic acidand/or phosphate salts. Other possible catalysts may include hydroxylcompounds, carboxyl compounds, organometallic compounds, alkaline metalcompounds, or ammonium or amine compounds. For example, possiblecatalysts include zinc, titanium, aluminum, and tin organometalliccompounds, alkaline metal or ammonium halides, aliphatic and aromaticamines, or other compounds such as boron complexes. In some exampleswhere polyurethane chemistry is involved certain catalysts likedibutyltin dilaurate (DBTDL) could be used. In some examples, thecomposition is cured by a thermally initiated curing process using aperoxide initiator.

Table 1 below provides various example formulations. These examples maybe utilized as binder systems, e.g. for stone composites. The systemsand/or composites may be solvent based or non-solvent based, asillustrated below. Some of these examples use Epoxol® 9-5 as an exampleepoxidized linseed oil, which is commercially available from ACSTechnical Products. Epoxol® 9-5 is a non-volatile, nonionic, nearlywater white polyepoxide with virtually no odor or flavor. Its typicalproperties include 9.0-9.5% of Oxirane Oxygen, an Iodine Value of 2-5, aGardener Color of less than 1, a Gardner Viscosity at 25° C. of 880 cps,a Specific Gravity at 25°/25° C. of 1.020. Epoxol® 9-5's ratio offunctionality sites per epoxy molecule of 5.5, and a molecular weight ofapproximately 980 Daltons. Epoxol® 9-5 is soluble in various hydrocarbonsolvents, particularly polar hydrocarbon solvents, including acetone orother ketones, alcohols, Carbon tetrachloride, chloroform,trichloroethylene, benzene and other aromatic hydrocarbons, and ethers.It is insoluble in water, hexane, mineral oil, and other aliphatichydrocarbons. Other linseed oils or other oils may be utilized, however.

Another example oil suitable for use in the formulations andcompositions is, as illustrated below in Table 1, is Epoxol® 7-4, anexample epoxidized soybean oil, which is commercially available from ACSTechnical Products. Epoxol® 7-4 is a non-volatile, nonionic, nearlywater white polyepoxide with virtually no odor or flavor. Its typicalproperties include 7.0-7.5% of Oxirane Oxygen, an Iodine Value of 1-3, aGardener Color of less than 1, a Gardner Viscosity at 25° C. of 500 cps,a Specific Gravity at 25°/25° C. of 0.995. Epoxol® 7-4's ratio offunctionality sites per epoxy molecule of 4.5, and has a molecularweight of approximately 960 Daltons. Epoxol® 7-4 is soluble in varioushydrocarbon solvents, particularly polar hydrocarbon solvents, includingacetone or other ketones, alcohols, carbon tetrachloride, chloroform,trichloroethylene, benzene and other aromatic hydrocarbons, and ethers.It is insoluble in water, hexane, mineral oil, and other aliphatichydrocarbons. As illustrated by the example oils, Epoxol® 9-5 containsabout 30% more oxirane oxygen than the example epoxidized soybean oiland therefore, about 30% more functionality on an equal weight basis.This, depending on the desired properties of the composite orcompositions, can result in greater performance and/or efficiency, ascan use of other high oxirane content oils. In other applications, alower oxirane content may be desirable, however, based on, e.g. the acidcontent of the resin material(s).

These example formulations also utilize various example acrylic resins.Many other acrylic resins, or other types of resin materials, may beutilized, however. In some examples, the resin material includes one ormore solid acrylic resins (e.g. a flake resin), or one or more high acidresins (but low acid resins may also be utilized). Resins with a varietyof molecular weight may be used, as described above. In some examples,the resin will have an acid equivalent weight of about 100 or more,about 150 or more, about 200 or more, about 250 or more, about 300 ormore, about 350 or more, about 400 or more, about 500 or more, about 600or more, about 700 or more, about 800 or more, or about 900 or more. Incertain embodiments, the acrylic resin having an acid value of about 20or more, about 35 or more, about 40 or more, about 45 or more, about 50or more, about 60 or more, about 75 or more, about 100 or more, about150 or more, about 200 or more, about 225 or more, about 250 or more,about 275 or more, about 300 or more, about 325 or more, about 350 ormore, about 375 or more, about 400 or more, about 450 or more, about 500or more, about 550 or more, about 600 or more, about 650 or more, orabout 700 or more. In some examples, the resin acid value is in a rangewith one of these values as the approximate upper limit, and anotherlower value may be a approximate lower limit (e.g. 75-375). The resinmaterial may have an acid value of about 35 to about 350, about 40 toabout 700, about 40 to 350, about 50 to 350, about 50 to about 300,about 35 to about 100, about 100 to about 250, about 150 to about 225,about 75 to 350, about 100 to about 350, about 200 to about 350, about75 to about 700, about 75 to 350, about 150 to about 700, about 200 toabout 700, about 150 to about 350, about 200 to about 375, or about 150to about 500.

TABLE 1 Oxirane Ingredients AV Percentage Tg Wt Wt % Comments ExampleFormulation # 1 Acrylic resin 70 — 62 40 82.5 Solid Flake CarboxylAcrylic Resin with an acid equivalent weight of about 800, and amolecular weight of about 10,500 Daltons Epoxol ® 9-5 9.4 — 8.4 17.5Source: ACS Technical Products Example Formulation # 2 Acrylic resin 215— 67 26.1 60.5 Acidic acrylic resin with an acid equivalent weight ofabout 260 and a molecular weight of about 4,500 Daltons Epoxol ® 9-5 9.4— 16.8 39.5 Source: ACS Technical Products Example Formulation # 3Acrylic resin 238 — 56 23.6 58.1 Acrylic resin with an acid equivalentweight of about 235, and a molecular weight of about 1,700 DaltonsEpoxol ® 9-5 9.4 — 16.8 41.9 Source: ACS Technical Products ExampleFormulation # 4 Acrylic resin 70 — 62 40 77.6 Solid Flake CarboxylAcrylic Resin with an acid equivalent weight of about 800, and amolecular weight of about 10,500 Daltons Epoxol ® 7-4 7.1 — 11.41 22.4Source: ACS Technical Products

An example formulation of a binder system using partial solvent as aprocessing aid follows below in Table 2.

TABLE 2 Ingredients Amt (g) Wt % Acrylic resin (acid equivalent 39.258.2 weight of about 260 and a molecular weight of about 4,500 Daltons)Acetone (solvent) 28.1 Epoxol ® 9-5 28.8 41.8 Total 96.1 % NV: 70%

As one example of a formulation process, 11.33 g of the above mixturewas placed in a glass jar and 77.5 g of quartz (using Hipu QS 005Fcommercially available from Gebrüder Dorfner GmbH & Co. as an examplequartz material, but other quartz sources or fillers may be used(including but not limited to sand or glass materials)) was slowlyadded, with constant mixing using a jiffy blade, for 5-10 min. Once thequartz was thoroughly wetted with the resin epoxy mixture, 35 g of thepasty mix was removed and spread on a Teflon sheet and dried in an ovenat 80° C./40 min. The dried materials was lightly ground with a mortarand pestle into smaller clumps, and these were used to progressivelyfill a stick mold at 80-100° C., pressing down layer by layer. The moldwas heated at 150° C. for 5 min and the mold lid was then placed on topof the mold. The material was then pressed under 12-13 T of pressure at150° C. for 90 minutes to cure. The final sample Barcol Hardness at roomtemperature was 70-80. Other temperatures, pressures, and/or cure timesmay be used as appropriate, based on the desired end characteristics,base ingredients, and/or amounts used.

Other example composites and curing processes, and example properties ofthe same, follow below in Table 3.

TABLE 3 Ingredients Formulation 1 Formulation 2 Quartz (100-315μ)  65 g77.5 g  Acrylic Resin (with Acid 6.5 g 5.0 g Value of about 215 and amolecular weight of about 4,500 Daltons) Epoxol ® 9-5 4.7 g 3.6 g CureTemp. ° C./min 150/90 150/90 Flexural Strength (psi) 7803 7736 BarcolHardness 70-80 70-80

As illustrated by the examples, the composites may have a flexuralstrength of, for example, about 7700 psi or more. In other examples, theflexural strength may be about 1000 psi or more, about 2000 psi or more,about 3000 psi or more, about 4000 psi or more, 5000 psi or more, about6000 psi or more, about 7000 psi or more, about 8000 psi or more, about9000 psi or more, or about 10,000 psi or more, or about 10,500 psi ormore.

Another example composite and curing process follows below in Table 4.

TABLE 4 Ingredients Amount Quartz (100-315μ) 86.7 g  Polyester Resin(Acid Value 6.3 g of about 351) Epoxol ® 9-5 3.4 g Cure Temp. ° C. / min150/90

The above table reflects an example of a stone composite applicationthat is solvent based. A more detailed explanation of this examplecomposition and an example process of making such a composite followsbelow.

In this example, a carboxyl functional polyester resin with an acidequivalent weight around 350 was synthesized using Cyclohexanedicarboxylic acid (CHDA), isophthalic acid, trimethylolpropane, 1,4butane diol and neopentyl glycol at individual percent compositionbetween 5-60%, using regular polyester synthesis procedure involving atin based catalyst. The resin was cut in acetone to make a 76% resinsolution. 8.3 g of the polyester resin solution was thoroughly mixedwith 3.4 g of EVO with 9.5% oxirane content and 86.7 g of high purityquartz QS005F. The mixture was then dried @ 80° C./1 hr. The dry mixturewas transferred to a mold where the material was compressed and heatcured under pressure at 150° C. for 90 minutes. The sample density oncooling to room temperature was 2.23 with a Barcol hardness of 65-70.The flexural strength of the sample according to ASTM method D 790 was4219 psi.

With suitable choice of ingredients (for example, quartz granules ofdifferent sizes to obtain higher loading and compaction) and fabricationtechniques other composites may have increased, or decreased, mechanicalproperties depending the goals and requirements of the application.

Another example of a stone composite application utilizes EVO and apolyester resin. In an example, the composite includes 92.7 g of quartzfiller (Hipu-QS005F), 2.3 g titanium dioxide R-700, 7.9 g PolyesterResin (acid equivalent weight of about 779 and a Tg of 57 C), 0.1 gAerosil 200, and 1.9 g EVO (168 Eq. wt.). The cure time is 60 minutes,and the cure temperature is 150 degrees Celsius. This example has awater absorption of 0.03% in 24 hours, and a 0.1% water absorption in 7days. The density is 2.34 g/cm³. The Barcol hardness is 70-80, and theflexural strength was 10,300 psi.

Another example application is liquid coatings, for example when epoxymaterial(s) and resin materials(s) are dissolved in a solvent, such asan organic solvent, to form a liquid coating. The coatings may behigh-solid liquid coatings. Example coating applications include usewith steel coils or for automotive and/or industrial finishes.Compositions, such as binder compositions, may be pigmented or clear. Insome examples, a binder composition or other composition may bedissolved, e.g. in a polar solvent, and then cured to give a high gloss,durable finish.

An example liquid coating embodiment follows below in Table 5.

TABLE 5 Ingredients Eq. wt Amt (g) % wt Acrylic Resin (acid equivalentweight 800 39.2 58.2 of about 260 and a molecular weight of about 4,500Daltons) Epoxol ® 9-5 171 28.1 41.8 2-Butoxyethanol (solvent) 20Dipropylene Glycol Methyl Ether 5 Acetone 2.5 Post-added Irganox ® 10100.11 BYK ®-019 0.1 Alkyl Imidazole Catalyst 0.3

In this example, the epoxidized linseed oil with 9.5 oxirane value wasmixed with 20 g of 2-Butoxyethanol solvent and 5 grams of dipropyleneglycol methyl ether, then 39.2 g of acrylic resin material was added(but other oils, resins, solvents, and amounts may be used). Then, 2.5 gof acetone and 0.4% of catalyst (alkyl imidazole) was added, and themixture was mixed until clear (again, other solvents, catalysts, andamounts may be used). Then a defoamer (in this example, BYK®-019,commercially available from BYK USA Inc.) and an antioxidant (in thisexample, Irganox® 1010, commercially available from BASF Corporation)were added (again, in other examples, other defoamers and/orantioxidants, and amounts thereof (including none) may be used). Asmooth film was then drawn down on cold rolled steel. The panel dried to1.5-2.0 mils at room temperature overnight (but other thicknesses anddrying times/conditions may be used, such as thickness of 0.3 mils ormore, 0.5 mils or more, 0.75 mils or more, 1.0 mils or more, 2.0 mils ormore, 3.0 mils or more, or 5.0 mils or more). The panel was then curedin the oven at about 150° C. for about 35 min (again, other times,temperatures, and conditions may be used). The cured coatings were clearwith high gloss and had excellent hardness, impact resistance, and stainresistance, along with chemical resistance of 100 acetone double rubs(ADR) with no burnish.

Example coating compositions may exhibit excellent adhesion properties.Thus, besides the outstanding adhesion of the cured films tosubstrate(s), such as but not limited to metal substrate(s), otheradhesive applications are possible. In one example a 0.5″×0.5″×2.5″acrylic/ELO quartz composite sample was intentionally fractured alongits length in the center. The acrylic/ELO solvent based solution wasapplied to the fractured area. The solvent was then allowed to evaporateat 80° C. and the warm parts were rejoined under limited pressure tosqueeze out excess adhesive. The sample was cured in the oven at 150° C.for 1 hour and then cooled. When tested for mechanical strength, thesample fractured at a different location at 1888 psi of force suggestingthat the adhesive strength was stronger than the composite sample.

Another example liquid coating embodiment follows below in Table 6.

TABLE 6 Ingredient Eq Wt. Amt(g) Polyester Resin (acid equivalent 77936.4 weight of about 779 and a Tg of 57 C.) ELO 9-5 168 8.4 MEK 24.5 BC4.0 Zinc phosphonium salt catalyst 0.5 Irganox ® 1010 0.2 Total: 74 Filmproperties Film drawdown air dried overnight. Cure Temp.: 150 C./1 hr.1N NaOH 24 hrs spot test: No effect 2% H₂SO₄ 24 hrs spot Test: No effectMEK double rubs: 200+ Hardness: 3H

In another example application, a composite may be a non-hazardous,solvent-free composite with a high degree of bio-renewable content(other examples may only have a subset of these properties, e.g. asolvent-free composite, or a non-hazardous composite). In otherexamples, the final composite is substantially solvent-free. In someexamples, the degree of bio-renewable content is 0-50% by weight. Insome examples, the degree is 5% by weight or more, 10% or more, 20%,30%, 40%, 50%, or 60% or more.

In this example application, a resin binder matrix for stone compositesmay use one or more fillers such as glass, crystalline silica such asquartz or similar materials, titanium dioxide, carbon fiber, amorphousprecipitated or fumed silica, ceramic, wood, or metals. In some examplesof a non-hazardous composite, the composite is solvent free or has verylow VOC mixture of carboxylic functional acrylic or polyester resin(e.g. a resin with MWt: 500-25000, AV: 50-275) and epoxidized oil orderivative with oxirane content 3.5-11.5%. In embodiments, the acrylateresin is a polymer formed from the free radical polymerization ofmonomers such as, but not limited, to styrene, MMA, BA BMA, acrylicacid, methacrylic acid, maleic anhydride, HEMA, HEA, and/or GMA(Glycidylmethacrylate) using, e.g., a free radical initiator. A polyester resinmay be formed by the condensation reaction of carboxylic and hydroxylgroups. This type of polyester will have a high proportion of carboxylicgroups and may contain hydroxyl groups. In some examples, the polyesterhas as few hydroxyl groups as possible, however. The epoxidized oil orits derivatives may contain oils, such C5-C26 aliphatic chains, whichmay have ester and internal epoxy groups.

Solvent free systems beneficially avoid air emissions and/or expensivesolvent recovery equipment while the addition of a catalyst speedscuring times. A composite binder composition consisting of a derivativeof an epoxidized oil that is thermally initiated and free radicallycured and the binder components may have very low VOCs. These types ofcompositions are differentiated from conventional styrene basedcompositions where the reactive diluent is volatile and toxic. Othercompositions may also have low VOCs.

In an example, a composition includes or consists of partially or fullyacrylated epoxidized vegetable oil between 0-50% by weight, amultifunctional acrylate between 10-40% by weight as a reactive diluent,including but not limited to trimethylolpropane triacrylate or 1,4butanediol diacrylate (BDDA), and a low molecular weight carboxylicfunctional acrylic or polyester resin between 10-50% by weight, with orwithout a liquid anhydride such as methyl hexahydrophthalic anhydride(mHHPA) between 0-30% by weight (where these illustrative weight rangesare for the relative amounts of these example components, and othercomponents such as fillers would impact the overall weight percentagesof a final product). The liquid components may act as a reactive diluentto assist in the application and wetting of the quartz or other fillers.The fillers and/or other additives may be added in various amounts, asillustrated by this disclosure. In an embodiment, after combining themixture with a free radical initiator such as the thermal peroxideinitiator Luperox® 101 and heat curing at 120-175° C., the result is ahard composite. Example compositions of this disclosure do not use anyanhydride, or only use small amounts such as about 30% or less byweight, about 25% or less, about 20% or less, about 15% or less, about10% or less, about 7.5% or less, about 5% or less, about 3% or less,about 2.5% or less, about 2% or less, about 1.5% or less, or about 1% orless (based on the total weight of the epoxy, acrylic or polyesterresin. and anhydride materials). Use of carboxyl functional resins suchas polyester, or a polyacrylic, which can optionally have anhydridegroups grafted to the polymer back bone will react directly withepoxidized vegetable oils. Thus, the anhydride is completely optional(and may be eliminated entirely or only presented as a minor component,e.g. may only be present in small amounts, e.g. about 5% or less, about2% or less, about 1% or less, about 0.5% or less, or about 0.25% orless, by weight, of the resin material), and these examples eliminateBPA based epoxies which tend to have a different cure behavior and havepoor UV durability. Example compositions may also be free of polyethersegments.

As another example, one that does not utilize a volatile solvent orvolatile reactive diluent, the carboxylic or anhydride functionalpolyester resin, carboxylic functional acrylic resin, or polyacid (orother resin material(s)) is in dry powdered form. In this example, thepowdered reactant remains suspended in the liquid EVO (or otherepoxidized oils/derivatives). As the temperature of the mold is raisedthe powder melts, reacts, and fuses in the binder formulation to give ahard cured product. In some examples, a powder resin material(s) is usedfor the composition. In certain of embodiments, the particle size of apowdered resin is smaller than the particle size of any fillers (e.g.under 500 microns, or in a size ratio of about 1:10 or less or 1:5 orless of resin powder size to filler powder size). A low viscosity liquidepoxy material may be used (e.g. ELO or ESO) with the powdered resin,where this may be heated to help lower the viscosity to, e.g., 1000 cpsor less, 800 cps or less, 600 cps or less, 500 cps or less, 300 cps orless, or 100 cps or less. The epoxy material may be added to the resinprior to the addition of fillers. The epoxy material may be added to wetthe fillers, and then a powdered resin is added. The epoxy/resin/fillercombination (however formed) may then be heated and/or compressed. Thiscan provide a solvent-free composition such as a composite.

An example of a solvent free or very low VOC composition with ELO uses5.0 g of acrylic resin with an approximate molecular weight of 1700, anacid equivalent weight of 235, and a Tg of around 55° C. was mixed with5 g of BDDA and 5 g of HHPA and 10 g of Epoxol 9-5 having 9.5% oxiranegroups to make a clear resin solution. The 10.8 g of the resin solutionwas then mixed with 0.06 g of 20% solution of Luperox 101 in acetone,0.1 g of glycerol, along with 0.027 g of 50% solution of an alkylimidazole catalyst in methyl ethyl ketone (MEK). To this, 89 g of Q005Mquartz (particle size 0.1-0.7 mm) was added and mixed for 25 min. Thequartz resin mixture was then transferred to a mold (0.5″×0.5″×2.5″cavity) at room temperature by packing it progressively layer afterlayer. The mold was closed with a pressure of 12 tons of force and heatwas applied. The mold was kept under the pressure at 130° C. for 1 hour.The mold sample was removed and post cured at 150° C. for 1 additionalhour. The sample was tested at room temperature and had a flexuralstrength of 4524 psi and density of 2.13 g/cm³.

Another example, utilizing ELO and CHDA, includes 3.9 g ofCyclohexanedicarboxylic acid (CHDA) with an acid value around 652 fromEastman Chemical, 8.4 g of Epoxol 9-5 with 9.5% oxirane, and 49.2 g ofQ005M quartz (particle size 0.1-0.7 mm). These ingredients are mixedthoroughly. The dough like mixture was transferred to a stick mold(0.5″×0.5″×2.5″) cavity. The mold was closed with a pressure of 12 tonsof force and heat was applied. The mold was kept under the pressure at163° C. for 90 minutes. The sample was tested at room temperature andhad a flexural strength of 2878 psi and a density of 2.08 g/cm³.

Additional examples of solvent free, fine powder compositions, wherethese examples use Epoxol 7-4 and Epoxol 9-5, follow below in Table 7.

TABLE 7 Eq. Epoxol 7-4 Epoxol 9-5 Wt. Compoistion CompoistionIngredients Acrylic Resin (acid 261 5.1 g 7.8 equivalent weight of about260 and a molecular weight of about 4,500 Daltons) (fine powder) Epoxol7-4 ESO 222 4.4 g — Epoxol 9-5 ELO 171 — 4.9 Zinc phosphonium salt 0.2 g0.3 catalyst Quartz, 0.1-0.71 mm 90.7 g 100.4 (Q005M) Titanium Dioxide(R-700) 1.7 g 1.0 Aerosil ® 200 Fumed 0.8 g Silica Acematt ® TS-100 0.15Thermal Silica Total: 102.9 g 114.55 Cure Temp/Time: 155° C./35 min.150° C./45 min. ° C./min Properties Density 2.33 g/cm³ 2.31 g/cm³ BarcolHardness 70-75 80-82 Flexural strength 5404 7688 (ASTM D790)

An example of an acrylated soybean oil based composite, made with freeradical cure, is detailed below in Tables 8-10.

TABLE 8 Example Composite Binder Formulation Ingredient Amt(g) Carboxylfunctional Acrylic 2.5 resin (4,500 MWT, Tg 65° C.) TMPTA (100%) 3.0Ebecryl ® 5848 (Acrylated 4.0 Epoxidized Soybean Oil) ELO 9-5 1.5 Zincphosphonium salt catalyst 0.1 Luperox ® 101: 20% in MEK 0.05 Total 11.15

TABLE 9 Example Composite Formulation Ingredient Amt(g) Quartz (Q005F)110 TiO2 (R700) 1.2 Aerosil ® 200 0.4 Binder formulation from Table 11.18 above Total 122.7 Cure Temp/time: 150° C./60 min.

TABLE 10 Properties Properties: Water absorption: 1.3% in 24 hoursBarcol Hardness: 70 Density: 2.20 g/cm³ Flexural Strength: 1206 psi

In another example application, aqueous coatings and/or adhesives may beprepared, for example when epoxy material(s) and resin material(s) aredispersed in water to form an aqueous coating dispersion. In someexample, a dispersion includes one or more stabilizing components. Thestabilizing component may be a neutralizing component(s) that stabilizesthe dispersion by neutralizing the dispersion. The neutralizingcomponent(s) may include one or more inorganic bases of ammonia, sodiumhydroxide, potassium hydroxide, one or more organic bases oftriethylamine, dimethylethanol amine, one or more Lewis bases. Thestabilizing component may be one or more anionic surfactants, one ormore nonionic surfactants, one or more neutralizing components, or acombination of the same.

As one example, a high acid value acrylic (e.g. MW: 1000-50000) and EVO(% oxirane 3.5-11.5) system can also be dispersed in water to give lowVOC systems suitable for coating or adhesive applications. The use ofwater based compositions has several advantages. For example, suchsystems have lower VOC levels, a reduced fire hazard compared to solventbased systems, lower worker exposure hazards, and faster dry time due tothe use of two phase systems. In some examples, the VOC content is about5.0 Lb/Gal or less, about 4.0 Lb/Gal or less, about 3.5 Lb/Gal or less,about 3.0 Lb/Gal or less, or about 2.5 Lb/Gal or less. An acrylic resinmay be mixed or partially reacted with the EVO (or other oil) or itsderivatives (e.g. epoxidized alkyl ester) followed by mechanically andspontaneous dispersion in a basic aqueous solution assisted by theaddition of a water miscible solvent. The solvent may be a higherboiling solvent like butyl cellosolve that can be also used to assist infilm formation and final appearance, or may be a highly volatile solventsuch as acetone which is later removed or stripped out after the mixturehas been dispersed.

Upon film formation, EVO (or another oil, as this disclosurecontemplates substitution or replacement of types of oils (e.g. EVO v.ELO) and/or or its types of oil) and/or its derivatives can act as areactive diluent that may react by heat assisted curing to give highlydurable films with a good appearance. The Tg and the acid value of theacrylic may be manipulated to give soft, hard, or tough impact resistantfilms. Suitable bases used for neutralizing include TEA(trimethylamine), DMAE (dimethylaminoethanol), and ammonia which can bepre-added to the resin or to the aqueous portion of the system. Heat andagitation may also be used for the dispersion process. The processallows for formulating compositions having smooth, high gloss films withor without solvent. The EVO can also act as a plasticizer to assist infilm formation. The non-volatile solids content of these systems can befrom 10-50% and result in films that can have high clarity and/or gloss.

Aqueous compositions may also be used for adhesive applications. Thematerial may be coated to one substrate, or one or more surfaces of asubstrate, and then air dried to form a tack free film. Anothersubstrate can be subsequently placed on the film and the two parts maybe adhered by heating and/or pressure to initiate the reaction betweenthe carboxylic group and the oxirane groups and therefore curing thematerials. This may result in a tough, heat resistant bond between thetwo surfaces. It may also allow large substrates and/or composite partsto be coated (partially or entirely) at one facility and cured atanother. The non-hazardous nature of the application is advantageous inlimiting worker exposure hazards. In some examples, an epoxy/resincomposition is applied to one or more substrates in either liquid orpaste form, and the one or more substrates are then joined to anothersubstrate, and the joined substrates are heat cured to adhere thesubstrates together.

This approach is also suitable for example uses with water based acryliclatexes. For example, a composition consisting of a high acid value(e.g. AV: 25-250) aqueous acrylic latex (e.g. 100 parts), 2-20% of EVO,2-20% of an EVO derivative such as epoxidized methyl soyate (EMS) orepoxidized methyl linseedate (EML), a catalyst, and a co-solvent (2-30%)may be air dried and thermally cured to give tough, solvent resistantcrosslinked films with a high bio-renewable content. Other amounts,components, and/or proportions may also be used.

As one particular example, 9.4 g of EVO with 9.5% oxirane content wasmixed in 25.5 g of acetone followed by addition of 40 g of a carboxylfunctional acrylic resin (MW: 10,500, Tg of around 55, and carboxylequivalent wt. around 800). The resin was dissolved over 2 hours to forma clear solution. The percent non-volatile was measured at around 72.5%due to a limited amount of solvent evaporation during the processing. Asolution was prepared where 0.3 g of 50% ammonia was added to 10 g ofwater at around 60° C. To the ammonia solution, 10.5 g of the aboveresin mixture was added under good agitation. The resin spontaneouslydispersed to form a translucent dispersion. Small amounts of additionalwater and ammonia were added to keep the solution basic. After warming,the acetone was then removed under vacuum conditions to give a stabledispersion with a pH of 7.37 and having 41% non-volatiles. Films drawndown on metal and glass were smooth and had high gloss, were wellcoalesced, and produced clear, fast drying, and tack free films. Thefilms were then heat cured at 150° C. for one hour to give hard, highgloss films.

As another example, Epoxol 9-5 and carboxyl functional acrylic resin(MW: 10,500, Tg of around 55, and carboxyl equivalent wt. around 800)were formulated into solvent based white and black pigmented coatings(in other examples, other pigments, dyes and/or colors may be used),along with top coat formulations pigmented white and black as controls.In these examples, a titanium dioxide was used as the white pigment, ata level of 20% PVC, and a carbon black pigment dispersion was used in anabout of 1.5% PVC. Other amount of dyes/pigments/colorants may be used(e.g. 3.0% carbon black dispersion). The formulations were drawn down onsteel test panels and heat cured at 160° C. for 60 minutes. Examplecontrol compositions and disclosure embodiments follow below in Tables11-14. The acrylic-melamine control paints were formulated at a 70/30polyol/melamine resin solids ratio catalyzed with 0.25% blocked p-TSAcatalyst on solids. The test example acid-epoxy paints were formulatedat a 58/42 acid/epoxy resin solids ratio catalyzed with 1.8% zincphosphonium salt catalyst, supplied by ACS Technical Products.

TABLE 11A Control White Pigmented Joncryl 500 and Cymel 303 Top CoatStep Ingredients & Instruction Quantity(lbs.) % Wt. % Vol. 1. GRIND BASFJoncryl 500 303.45 26.99 35.3 Methyl n-Amyl Ketone (MAK) 42.04 3.74 6.18Add enough MAK to achieve good vortex then slowly add: BYK AdditivesDisperbyk 180 8.03 0.71 0.89 Chemours Ti-Pure R-706 398.55 35.46 11.94MAK 0.00 0.00 0.00 Add enough MAK to achieve good vortex & grind on HSDto 7+ Hegman 2. LETDOWN BASF Joncryl 500 89.69 7.98 10.43 Allnex Cymel303 LF resin 135.09 12.02 13.49 Premix next 3 ingredients & add:n-Butanol 33.82 3.01 5.00 King Industries Nacure 2500 4.48 0.40 0.55 BYKAdditives BYK-358N 5.42 0.48 0.68 Reduce viscosity to 70-75 KU with thefollowing: Methyl isobutyl ketone (MIBK) 103.52 9.21 15.52 TOTALS1,124.10 100% 100%

TABLE 11B Properties of Table 11A Composition Physical PropertiesCalculated Value % PVC 19.99 % Weight Solids 76.13 % Volume Solids 60.45Specific Gravity (g/cm3) 1.347 Weight/gallon (Lb/gal) 11.24 VOC (Lb/Gal)2.68 VOC (g/L) 321.6

TABLE 12A Test White Pigmented Epoxol 9-5 and Acrylic Resin Topcoat ItemCode Ingredients & Instruction Quantity(lbs.) % Wt. % Vol. 1. GRINDAcrylic Resin (4,500 MWT, Tg 66, 210.61 20.87 24.50 Carboxyl Eq. Wt.260) in MEK (64.7%) MEK 29.31 2.90 4.37 Add enough MEK to achieve goodvortex then slowly add: BYK Additives Disperbyk 180 5.83 0.58 0.65Chemours Ti-Pure R-706 292.29 28.97 8.76 MEK 41.68 4.13 6.21 Add enoughMEK to achieve good vortex & grind on HSD to 7+ Hegman 2. LETDOWNAcrylic Resin (4,500 MWT, Tg 65, 62.93 6.24 7.32 Carboxyl Eq. Wt. 215)Epoxol 9-5 ELO 126.98 12.58 14.77 Premix next 3 ingredients & add DowChemical Dowanol DPM 26.12 2.59 3.29 Zinc phosphonium salt catalyst 5.560.55 0.67 BYK Additives BYK-358N 4.31 0.43 0.54 Reduce viscosity to70-75 KU with the following: Eastman Glycol Ether EB 86.76 8.60 11.53MEK 116.72 11.57 17.40 TOTALS 1.009.10 100% 100%

TABLE 12B Properties of Table 12A Composition Physical PropertiesCalculated Value % PVC 19.98 % Weight Solids 60.32 % Volume Solids 44.98Specific Gravity (g/cm3) 1.209 Weight/gallon (Lb/gal) 10.09 VOC (Lb/Gal)4.0 VOC (g/L) 479.8

TABLE 13 Control Black Pigmented Joncryl 500 and Cymel 303 Top Coat ItemCode Ingredients & Instruction Quantity(lbs.) % Wt. % Vol. 1. MIX BASFJoncryl 500 477.3 56.4 55.5 Allnex Cymel 303 LF Resin 165.4 19.5 16.5MAK 51.3 6.1 7.5 Slowly add colorant and mix thoroughly: ChromafloTechnologies Chroma-Chem 66.3 7.8 7.8 844-9956 2. LETDOWN Premix next 3ingredients & add: n-Butanol 28.9 3.4 4.3 King Industries Nacure 25005.22 0.6 0.6 BYK Additives BYK-358N 3.32 0.4 0.4 Reduce viscosity to70-75 KU with the following: MIBK 48.7 5.8 7.3 TOTALS 846.3 100% 100%

TABLE 13B Properties of Table 13A Composition Physical PropertiesCalculated Value % PVC 1.56 % Weight Solids 68.04 % Volume Solids 60.61Specific Gravity (g/cm3) 1.014 Weight/gallon (Lb/gal) 8.46 VOC (Lb/Gal)2.7 VOC (g/L) 324.1

TABLE 14 Test Black Pigmented Epoxol 9-5 and Acrylic Resin Topcoat ItemCode Ingredients & Instruction Quantity(lbs.) % Wt. % Vol. 1. GRINDAcrylic Resin (4,500 MWT, Tg 66, 383.8 46.9 44.7 Carboxyl Eq. Wt. 260)in MEK (64.7%) Epoxol 9-5 ELO 178.2 21.7 20.7 MEK 42.6 5.2 6.4 Slowlyadd colorant and mix thoroughly: Chromaflo Technologies Chroma-Chem 54.86.7 6.4 844-9956 2. LETDOWN Premix next 3 ingredients & add: DowChemical Dowanol DPM 38.6 4.7 4.9 Zinc phosphonium salt catalyst 7.760.9 0.9 BYK Additives BYK-358N 3.11 0.4 0.4 Reduce viscosity to 70-75 KUwith the following: MEK 64.9 7.9 9.7 Eastman Glycol Ether EB 45.1 5.56.0 TOTALS 818.8 100% 100%

TABLE 14B Properties of Table 14A Composition Physical PropertiesCalculated Value % PVC 1.52 % Weight Solids 56.16 % Volume Solids 52.12Specific Gravity (g/cm3) 0.981 Weight/gallon (Lb/gal) 8.19 VOC (Lb/Gal)3.6 VOC (g/L) 430.1

Test Results for these compositions follow below in Tables 16 (whitecoatings) and 17 black coatings). The four coatings were applied tometal panels via wire wound rod application, allowed to set underambient conditions for one hour then baked for one hour at 160° C. witha 15-minute temperature ramp-up time. Three different metal substrateswere used including cold rolled steel, Bonderite 1000 phosphated steeland untreated aluminum. The panels yielded 1.0-1.3 mils dry filmthickness. Panels were tested for adhesion, hardness, solvent andchemical resistance, flexibility and impact resistance according toTable 15.

TABLE 15 Test Protocols Phos Physical Property Tests Test MethodAluminum CRS CRS Adhesion ASTM D3359 X X X Chemical Resistance ASTMD1308 X Flexibility by Conical ASTM D522 X Mandrel Flexibility by T-BendASTM D4145 X Gloss ASTM D523 X Hardness (Pencil) ASTM D3363 X ImpactResistance ASTM D2794 X MEK Resistance ASTM D4752 X

TABLE 16 Detailed Test Results of White Coatings Control Test WhiteWhite Test Baking Baking Physical Property Method Substrate EnamelEnamel Cure Schedule 60′ @ 60′ @ 160° C. 160° C. Average DFT (mils)1.0-1.2  1.0-1.3 Adhesion ASTM CRS 4A-5A* 5A D3359 4A-5A* 5A AdhesionASTM Phos CRS 5A 5A D3359 5A 5A Adhesion ASTM Aluminum 3A 5A D3359 3A 5AHardness (Pencil) ASTM CRS >6H  >6H  D3363 MEK Resistance ASTMCRS >200 >200 D4752 >200 >200 Gloss - 20° ASTM Aluminum 59.2 81.5Gloss - 60° D523 79.0 94.4 Gloss - 85° 96.9 97.9 Chemical Resistance -16- Hour Spot ** 10% Sulfuric Acid ASTM CRS 5 5 Xylene D1308 5 5Isopropyl Alcohol 5 5 Water 5 5 Flexibility by ASTM CRS Fail ¾″ Pass ⅛″Conical Mandrel D522 Bend Flexibility by ASTM Aluminum Fail 6T Fail 6TT-Bend D4145 Impact Resistance Direct ASTM CRS 20 Fail/ 80 Fail/ D279415 Pass 70 Pass Reverse 5 Fail 60 Fail/ 50 Pass *Coating chattersslightly upon scribing (Brittle) ** Observations - Severity Ratings: 5 =No effect, 4 = Slight Effect, 3 = Moderate Effect, 2 = Severe Effect, 1= Total Failure; Failure Modes: BL = Blistering, DL = Delamination

TABLE 17 Detailed Test Results of Black Coatings Control Test BlackBlack Test Baking Baking Physical Property Method Substrate EnamelEnamel Cure Schedule 60′ @ 60′ @ 160° C. 160° C. Average DFT (mils)1.0-1.2 1.0-1.3   Adhesion ASTM CRS 0A * 5A D3359 0A * 5A Adhesion ASTMPhos CRS 0A * 5A D3359 0A * 5A Adhesion ASTM Aluminum 0A * 4-5A D33590A * 4-5A Hardness (Pencil) ASTM CRS B >6H  D3363 MEK Resistance ASTMCRS 200 99 D4752 197 104 Gloss - 20° ASTM Aluminum 90.3 90.3 Gloss - 60°D523 97.2 94.1 Gloss - 85° 95.5 98.2 Chemical Resistance - 16- Hour Spot** 10% Sulfuric Acid ASTM CRS 5 5 Xylene D1308 1DL 5 Isopoply Alcohol 55 Water 5 5 Flexibility by ASTM CRS Fail 1½″ Pass ⅛″ Conical MandrelD522 Bend Flexibility by ASTM Aluminum Fail 6T Fail 6T T-Bend D4145Impact Resistance Direct ASTM CRS 5 Fail 70 Fail/ D2794 60 Pass Reverse5 Fail 80 Fail/ 70 Pass * Coating chatters slightly upon scribing(Brittle) ** Observations - Severity Ratings: 5 = No effect, 4 = SlightEffect, 3 = Moderate Effect, 2 = Severe Effect, 1 = Total Failure;Failure Modes: DL = Delamination, GL = Gloss Loss

For the white coatings, both the control and test coating showed goodadhesion to steel and phosphated steel, excellent hardness, acid, waterand MEK resistance. The test coating was superior to the control inadhesion over aluminum, flexibility and impact resistance. The testcoating also showed higher 20° and 60° gloss than the control.

For the black coatings, both the control and the test coating showedexcellent gloss, acid, alcohol and water resistance. The test coatingwas superior to the control in adhesion to all substrates, hardness,flexibility and impact resistance. What's more, the black controlcoating showed severe adhesion loss when applied directly to thesubstrates when compared to the test coating.

In sum, the test coatings had good gloss, adhesion, hardness, MEK, acidand water resistance, mandrel bend flexibility and impact resistance.

Another example of a black coating composition follows below in Table18.

TABLE 18 Item Code Ingredients & Instruction Quantity(lbs.) % Wt. %Vol. 1. GRIND Acrylic Resin (4,500 MWT, Tg 66, 359.17 43.77 41.78Carboxyl Eq. Wt. 260) in MEK (64.7%) Epoxol 9-5 ELO 166.89 20.34 19.41MEK 39.89 4.86 5.94 Slowly add colorant and mix thoroughly: ChromafloTechnologies Chroma-Chem 102.54 12.50 12.05 844-9956 2. LETDOWN Premixnext 3 ingredients & add: Dow Chemical Dowanol DPM 35.94 4.38 4.53 Zincphosphonium salt catalyst 7.15 0.87 0.86 BYK Additives BYK-358N 5.830.71 0.74 Reduce viscosity to 70-75 KU with the following: MEK 60.967.43 9.09 Eastman Glycol Ether EB 42.23 5.15 5.61 TOTALS 826.60 100%100%

As another example, amino resins, such as Cymel® 303, may also be addedto composition (such as a binder composition) containing a carboxylfunctional resin (acrylic or polyester) to react with the hydroxylgroups generated from the epoxy ring opening to form a thermosetcomposition. Similarly, Polyisocyanates, isocyanate terminatedprepolymers, or blocked isocyanate version of the polyisocyanate orprepolymers, may also be included in the formulations. The amount (e.g.5-40% by wt.) may be based on the equivalent levels of epoxy groups inthe formulation. EVO derivative adducts with poly isocyanates may alsobe prepared by reacting the EVO containing hydroxyl groups. Theisocyanate can be aromatic or aliphatic, including but not limited toMDI or H12MDI or IPDI.

For a particular example of the above compositions, a carboxylfunctional acrylic was first dissolved in MEK followed by addition ofEVO, Cymel® 303 and a catalyst. The formulation was stirred continuouslyfor 1 hr. and allowed to sit overnight. Films were drawn on cold rolledsteel (CRS) followed by air drying for 1 hr. and placed in oven to cureat 150 Celsius for 55 min. The coating was tested for performance andhad excellent hardness, stain, solvent and chemical resistance alongwith high clarity and gloss. Composition and property information areprovided below in Table 19.

TABLE 19 Ingredients Wt (g) Acrylic resin (4,500 Mwt, Tg 66° C., AV: 2156   EVO (Epoxy eq. wt: 170) 3.9 Cymel 303 LF (Allnex) 2.2Zinc-Phosphonium salt (catalyst) 0.2 MEK 10.2  Total (% NV: 54.7%) 22.5 Cure: 150 C./55 min MEK DR 200+   Sharpie Marker Stain No effect NaOH(10%) overnight, 24 hrs No effect Hardness 6H Film Clarity clear

In another example applications, solvent free epoxidized vegetable oil(or other oil) based powder coating systems with tough, chemicallyresistant properties may be prepare for use on, e.g., metal substrates.These may also be utilized on other materials such as, but not limitedto, encapsulating engineered wood (MDF).

Conventional powder systems generally have virtually no volatilesreleased. However, the use of bisphenol-A based epoxy resins in thehybrid powder systems result in coatings that yellow and chalk greatlyon UV exposure. The widely used triglycidyl isocyanurate (TGIC)crosslinker is also toxic and classified as a Category 2 mutagen.

An acid value of less than 50 may limit the amount of the epoxycomponent that can be incorporated into the powder coating. A high acidvalue of the carboxylic functional resin gives increased crosslinkdensity, toughness, chemical and water resistance, impact resistance,and other desirable properties such as gloss for coatings as well ascomposites. On the other hand, a higher level of epoxidized vegetableoil (EVO) introduces tackiness in the powder coating formulation makingit less practical for the application of powder coatings.

In some examples, the EVO can be partially reacted with a carboxylfunctional molecule that can be either a polyester, an acrylic, or apolycarboxylic acid molecule like phthalic acid or similar molecules, togive compositions suitable for high performance powder coatingapplications. By partially reacting the acrylic resin and opening up theepoxy groups in the EVO, it is possible to advance the molecular weightand the physical state thereby reducing the plasticizing effect of theEVO thus allowing the use as a higher performing powder coating system.

The system may also be blended with glycidyl based acrylics instoichiometric amounts to optimize the performance for appropriateapplications. The optimized combination of glycidyl methacrylate (GMA)based acrylics with carboxyl functional acrylics with acid valuesgreater than 50, and partially reacted EVO, may be used in powdercoating applications. This may reduce costs by elimination of expensivelong chain diacid crosslinkers such as dodecanedioic acid, as well asreducing the amount of GMA based acrylics in the system. These types offormulations may be used in applications such as automotive clear coatsand specifically for automotive alloy wheels. The higher level offunctionality from the epoxidized vegetable oil will give improvedperformance without causing film brittleness or chipping, for examplefrom gravel and stones.

As one particular example, a partially reacted EVO and acrylic resinpowdered clear coat is prepared. In this example, 0.8 g ofcyclohexanedicarboxylic acid (CHDA) was mixed with 9.2 g of Epoxol 9-5ELO with 9.5% oxirane groups at 150° C. for 10 minutes. Next, 11.2 g ofcarboxyl functional acrylic resin with a molecular weight around 4,500and an acid value of around 215 and a Tg around 65° C. were added to thereactants and further mixed for 5 minutes at 130° C. The resin mixturewas then cooled below −15° C. and broken down to smaller pieces. Afterthe addition of 0.2 g of fine fumed silica powder to the resin pieces,the mixture was pulverized in a grinder into fine powder. The resultingpowder was filtered using a #80 sieve. The filtered powder was evenlyspread onto a 6″×4″ steel plate. Then the plate was baked in an oven at175° C. for 45 minutes. The particles fused to form a clear, hard filmwith good gloss. The film was highly chemically resistant and able towithstand more than 200 MEK double rubs without blemish.

In some process examples a matrix binder is created using two morecomponents, e.g. where one or more powdered resin materials (e.g. one ormore polyester and/or acrylic resin materials) are provided to act as amatrix for one or more filler materials, and fill in voids in thosefillers, such as quartz fillers. The powder materials may be heated(e.g. before being placed in a mold, or the mold itself containing thematerials is heated to soft and/or melt prior to compression) so theyliquefy and flow into the voids, which advantageously allows morecompression and enhanced mechanical properties. In some examples,additional materials such as one or more amino resin materials, are alsoincluded. In some examples, after some or all voids are filled, thecomponents are cured together to provide a dense composite.

In some example processes, a resin system with two or more componentsmay function as a matrix binder. A first component may be a liquidreactive diluent and a second component may be a solid polymer component(or a compound) in form of a powder that is capable of reacting with theliquid component. Thus, these process examples may utilize a drypowdered resin material. The reaction between the liquid and powdercomponents may occur at an elevated temperature. In some examples, thepowdered resin material is capable of melting and flowing at highertemperatures but below its threshold reactive temperature, thus allowingit to flow, diffuse and mix with the first component at its melttemperature. This approach allows ease and possibility of using a highermolecular weight resin and or a higher Tg polymer in the formulationwithout the use of a solvent.

The result of these process examples is a free flowing mixturecomposition. The flow of the powder at room temperature can be furtherenhanced with the use of one or more additional components, such as asolid material, e.g. fine silica. In some examples, the liquid componentis present in a smaller amount than the solid component in proportion.For example, in the liquid component may be present in an amount of 80%by weight or less, as compared to the amount of the powder component, or70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% orless, or 10% or less.

In certain examples of these processes, an epoxy based system is used,i.e. a liquid epoxy would act as the reactive diluent (the firstcomponent) and as a wetting agent. Example Physical Properties forsuitable liquid epoxy components include: a straw colored (APHA: 100);an epoxy Equivalent weight of 167-170; an acid value of <0.5; aviscosity @ 25° C./50° C. of 750/200 cps; a specific gravity @ 25° C. of1.030; and a flash point of 315° C.

The other component may be a higher molecular weight carboxyl functionalresin. In some examples, one or more fillers, such Quartz, TiO₂ andothers (such as other porous and/or non-porous fillers) are first wettedusing the liquid epoxy binder. The epoxy may then be warmed, e.g. toabout 50° C. or more (or other temperatures, based on the particularproperties of the epoxy and other processing variables) to lower theviscosity and facilitate mixing. In certain examples, the one or morefillers may be about 50% or more by weight of the entire composition,about 60% or more, about 70% or more, about 80% or more, about 90% ormore, or about 95% or more. In some examples, the liquid diluent (ordiluents) may equal to about 30% by weight or less of the weight ofentire composition, about 25% or less, about 20% or less, about 15% orless, about 10% or less, about 7.5% or less, about 5% or less, about 3%or less, about 2.5% or less, about 2% or less, about 1% or less, orabout 0.5% or less. In some examples, the powder resin (or resins) mayequal to about 60% by weight or less of the weight of entirecomposition), about 50% or less, about 40% or less, about 30% or less,about 25% or less, about 20% or less, about 15% or less, about 10% orless, about 7.5% or less, about 5% or less, about 3% or less, about 2.5%or less, about 2% or less, or about 1% or less.

In some examples, after the surface of the filler is substantiallyand/or completely wetted with the reactive diluent (and where,optionally, other wetting additives may be used to facilitate theprocess), the powdered resin (the second component) is added withcontinuous mixing (in other examples, this may be done concurrently).The composition may then be compacted, for example by a press and mayinclude vibration and/or vacuum to assist in compaction. The particlesize of the powdered resin may be smaller than the quartz fillers(and/or other fillers, as appropriate) to fill any voids, for examplethose created during a vacuum, vibration and compaction process. Oncethe compacted formulation is compressed and free of voids (or where atleast some voids are filled) the composition may then be cured at anappropriate curing temperature.

Moreover, catalysts may be mixed in or incorporated in the polymer orthe reactive diluent to assist the curing process. The result of theseexample processes is a hard composite with high mechanical and chemicalproperties.

In certain examples of the multicomponent process, the first componentmay contain a small amount of liquid anhydride in a non-stoichiometricamount (e.g. about 30%, 20%, 10%, 5%, or 3% or less by weight, based onthe weight of the major epoxy component). In some examples and thesecond component may have a partial amount of the liquid epoxy premixedwith the carboxyl functional resin and then ground into a fine powder.In these examples, sum of the reactive equivalent can be instoichiometric amounts though the total epoxy to carboxylic equivalentratio can vary, for example from about 0.5-1.5, about 0.9-1.5, about or0.7-1.7. In certain examples, the first component may be an acrylicand/or a polyester.

The above described multicomponent process may be applied to provide astone composite, but may also be applied for a variety of products, andmay utilize additional or other materials. For example, other resinmaterial(s) could be used such as those described throughout thisapplication. As one example, a liquid epoxy material, an amino resinmaterial, and a polyester material could be used together (or asub-group could be used together), for example in the proportionsdescribed elsewhere regarding coating embodiments. The above describedmulticomponent process may be applied with other systems and is notlimited to the above system examples. For example, a hybrid curingsystems or free radically initiated systems could similarly utilize thecomponents and applicable process steps illustrated above and throughoutthis disclosure.

In some examples, the first component is a reactive liquid component,which may have a relatively low viscosity product of about MWt 50-5,000Daltons (or other weights/weight ranges, such as about 150-2000, about500-1500, about 1000 or more, about 1500 or more, about 2,000 or more,about 1500 or less, about 1000 or less, or about 500 or less). In someexample, the second component may be a hard polymer or another reactivepowdered compound at room temperature. The MWt of this polymer may befrom about 100-25,000 Daltons, or about 200-20,000 Daltons.

In some examples, one or both components can optionally be doped withthe other component (or one or more different compounds of similarfunctionality) in non-stoichiometric amounts to facilitate uniformity ofreaction in the mold during curing, for example, a relative amount ofabout 30% by weight or less of the other component based on the weightof the main component (e.g. the liquid component is added in an amountequal to about 30% by weight or less of the weight of the dry component,or vice versa), about 25% or less, about 20% or less, about 15% or less,about 10% or less, about 7.5% or less, about 5% or less, about 2.5% orless, or about 1% or less. In some example, a small amount of eachcomponent is added to the other, for example in the amounts describedabove. In certain examples, a small enough amount is transferred suchthat there will not be any reaction between the components at the timeof doping.

The overall stoichiometry of the binder composition, in some examples,would be around 0.9-1.5, but the ratios may be adjusted within thisrange or outside of it for optimum performance of the cured product andprocessability.

As specific material examples, the first, liquid component, may includeone or more of the following, one or more bio-based epoxy materials, oneor more amino resin materials such as Cymel® 303, one or more liquidanhydride materials, and/or one or more poly acrylates (such as 1,4butane diol diacrylate), 1,4 butane diol, 1,6 hexane diol, and/or one ormore low molecular weight liquid polyethers. The example resin materialsmay be used as a doping material or materials in the liquid component,where the same or different resin material(s) may be used for the secondcomponent. In examples with multiple components in the liquid component,the one or more bio-based epoxy materials may be the major component(i.e. present in an amount of about 50% by weight or more of the totalweight of the combined liquid components, or about 60% or more, about70% or more, about 80% or more, or about 90% or more). As specificmaterial examples, the second, solid component, may include one or moreof the following: one or more carboxyl and/or hydroxyl functionalacrylics and/or polyesters, one or more solid anhydrides, one or moreGMA acrylics, and or one or more crystalline unsaturated polyesters. Insome examples a solid reactive component with functionality similar tothe reactive diluent or that of the second, solid component may bedissolved in the reactive diluent, for example at room temperature, orassisted by warming to help wet and coat the filler particles which oncooling can form a coated film on the particles. As one example, a solidepoxy component can be dissolved in a liquid epoxy component.

These and other examples of the multicomponent process provide theability to incorporate higher molecular wt. resins and therefore providevarious advantages. The multicomponent system eliminates the use ofsolvents, as one example, including the commonly used hazardousmaterials such as styrene. As another, the resulting compositions haveimproved performance properties, at least because there are fewermonomeric or mono functional chain terminating species. As anotherexample, the processes examples enable the formulator to use nontoxicformulations, and avoid the use of styrene as a reactive diluent. Asanother example, the process examples incorporate bio-based content. Asyet another example, the process examples, allow variance of mechanicaland chemical properties by changing the compositional structure andincreasing formulation latitude.

Example performance properties of compositions created by these examplesprocesses include: excellent hardness and good scratch resistance,excellent flexibility and impact strength, excellent adhesion to polarsubstrates and suitability for FRP products, excellent exteriordurability (unlike conventional BPA epoxies), provision of curedcomposites that are heat stable and have excellent water, alkali,chemical, solvent, and stain resistance, provision of formulationssuitable for application requiring high gloss and clarity, and use ofbio-based carbon content that is ecofriendly and has very low toxicity.

As examples, the two component process may include mixing a liquidreactive diluent with one or more fillers to coat or wet some or all ofthe surfaces of the one or more fillers, then mixing the coated fillerswith a reactive thermoplastic powdered resin. In some examples, a dry,powdered solid carboxylic functional acrylic resin material or a solidpolyester resin material with free reactive carboxylic groups is used.Then, in some examples, the process may include softening, compacting,and curing the mixture to provide a thermoset composite material. Thediluent, filler and powder mixture may be softened by heating, and thesoftened mixture may then be compacted, and then the compacted mixturemay be cured to have the reactive components react with each other. Insome examples, epoxy and resin materials may be heated near to, to, orabove the glass transition temperature or the melt temperature of theresin material to provide a free flowing mixture. In some examples,other or additional processing steps, such as vibration, may be used. Insome examples, multiple heating steps are used. In some examples, thematerials are mixed, placed in a mold or cast, compacted, heated tosoften, spread, and/or melt around the fillers and/or into any fillervoids, and compacted again. In some examples, the mixture is compactedwith a vacuum and vibration compaction process, in a mold or cast, orotherwise. In certain examples, the mixture is in a mold, that is thenpressed, for example in a heated press. In some examples, the materialis heated enough to soften the resin(s) but not melt them. In someexamples, the materials are heated to the resin Tg. In some examples,the order of steps is changed, or certain steps may be performedsimultaneously. In certain examples, the liquid diluent componentincludes or consists of an epoxy resin, an amino resin, or both. In someexamples, the thermoplastic powdered resin component includes orconsists of an acrylic resin, a polyester resin, an epoxy resin, a solidanhydride compound, or a polyacid compound. In certain examples, thereactive diluent includes or consists of an amino resin and the powderedresin includes or consists of an hydroxyl functional polyester and/or ahydroxyl functional acrylate.

In certain examples, the reactive diluent includes or consists of amultifunctional acrylate and/or a vinyl compound, and the powdered resinincludes or consists of an unsaturated polyester and/or acrylic resin.In various examples, the components are reacted and cured by a thermallyinitiated curing process, and the process may use a peroxide initiator.

In various examples, the reactive diluent includes or consists of apolyisocyanate, and the powdered resin includes or consists of one ormore of a hydroxyl functional acrylate, a hydroxyl functional acrylic,and/or a polyether polyol. Other components that are liquids at roomtemperature and will not react with the polyisocynantate at roomtemperature may also be used. In some examples, a catalyst in in theresin, e.g. a acrylic polyol, will be released when the resin melts. Inexamples with a catalyst releasing resin materials(s), relatively largeramounts of doping are possible, For example, using larger amounts ofliquid diluent may ensure complete wetting, without a concern aboutpremature reaction. In certain examples, the liquid reactive diluentincludes or consists of a vegetable oil based epoxy, for example anepoxy with an epoxy equivalent weight of about 150 to 250 (or about 150or more, about 175 or more, about 200 or more, about 225 or more, orabout 250 or more, or, about 250 or less, about 200 or less, or about150 or less). In certain examples, the powdered resin includes orconsists of an carboxyl functional polyester and/or acrylic with acidvalue of 50 to 350, or about 50 to 700, or about 50 or more, about 100or more, about 200 or more, or about 300 or more.

In certain examples, the powdered resin is doped with an amount of theliquid diluent sufficient to soften the physical state of the powderwithout plasticizing, agglomerating, or tackyifying the powder, fusingthe components together, and/or otherwise compromising the physicalstate of the powder. In some examples, the liquid diluent is doped withan additional liquid reactive component that includes one or more of thefunctional groups that are present in the powdered resin. In certainexamples of the process, one or more wetting agents like Disperbyk 2152or BYK-W 985 are added to the liquid diluent. In some examples, one ormore adhesion promotors are added to the liquid diluent, such as one ormore organosilanes compounds/silane coupling agents. In some examples,one or more wetting agents and one or more an adhesion promotors areadded to the liquid diluent. In various embodiments, the powdered resinmaterial(s) are mixed with silica, for example fine amorphous silica.The silica may have a size of less than about 0.10 microns, about 0.05microns, or about 0.03 microns. In certain examples, the particle sizeof the powdered resin material(s) is smaller than the particle size ofthe one or more fillers, or smaller than the particle size of at leastsome of the selected fillers. In certain examples, a liquid diluent,filler, and powdered resin mixture is melted by heat prior tocompaction, and in some embodiments, a liquid diluent, filler, andpowdered resin mixture is softened by heat prior to compaction.

In various embodiments, a liquid diluent, filler, and powdered resinmixture is subjected to a vacuum, a non-ambient pressure, vibration,heat, or a combination thereof. In certain examples, a catalyst is addedto a liquid diluent, filler, and powdered resin mixture, or isincorporated in one of the component materials, such as the powderedresin.

In some examples, a composite is provided, for example by one or more ofthe above process examples. In various embodiments, a thermosetcomposite material is made from a first liquid resin component and asecond thermoplastic powdered resin component that were reacted andcured to provide a solid, cross-linked matrix, and one or more fillersdispersed within the matrix. The matrix and fillers may be free orsubstantially free of voids, as explained above. In certain examples ofthe composite, the first liquid resin component includes or consists ofan epoxy resin, an amino resin, or both an epoxy resin and an aminoresin, and the thermoplastic powdered resin includes or consists of oneor more of an acrylic resin, a polyester resin, an epoxy resin, a solidanhydride compound, or a polyacid compound. The one or more fillers mayinclude or consist of quartz granules, marble granules, carbon fibers,carbon tubes, chopped glass or glass fibers, fabric, silica, ceramic, ora combination thereof. In certain examples, the equivalent ratio of thefirst and second resin components is between about 0.5 to 1.5, about0.75 to 1.25, about 0.9 to 1.1, or about 0.95 to 1.05 (or vice versa forany of these ratios). In some examples. The components may also have anequivalent ratio of about 1.

As a specific particular example of a multicomponent process asdescribed herein, quartz materials may be charged and TiO₂ material isadded in a mixer, such as a mixer fitted with an agitator suitable formixing dry solids. The materials may be mixed (for, e.g., about fiveminutes, or about ten minutes) to break down pigment agglomerates.XP-9500 (an epoxy resin available from ACS Technical Products) may beadded, and the components may be mixed (for, e.g., about five minutes orabout ten minutes) to ensure complete wetting of the sand and TiO₂.XP-5175 (a polyester resin with an acid equivalent weight of about 779and a Tg of 57 C available from ACS Technical Products) may then beadded as a powder under constant agitation for, e.g. about 10 minutes,to provide a uniform or substantially uniform mixture. The mixture maybe transferred to a mold and compacted, e.g. with the mold plunger byprogressively filling the mold and compressing the contents. The moldmay then be placed in a heated press, e.g. at about 160° C. or anothertemperature appropriate for curing the utilized materials. The mold lidmay be pressed down to squeeze out excess product from the bleedopenings under pressure. The composition may be cured for a timeappropriate based on the utilized materials, e.g. about 40 minutes. Theparts may then be removed form the mold and allowed to cool, for exampleto room temperature.

TABLE 20 Ingredients Amt Comments Quartz filler Hipu- 88.4 GebrüderDorfner GmbH & Co. QS005F TiO₂ R-700 2.2 DuPont ® XP-5175 7.6 ACSTechnical Products XP-9500 1.8 ACS Technical Products Total 100 Cure:160° C./35 min.

Sample properties of the above composition follow below.

TABLE 21 Binder Sharpie resistance to Flex. Water abs. Density Marker10% Caustic Barcol Str.(psi) RT (g/cm³) resistance soln.(16 hrs) 7810,300 7 days 0.1%, 2.27 No effect No effect 24 hrs: 0.03%

As discussed above, the compositions, formulation, and composites may beused in various systems and applications. For example, a component maybe partially or entirely covered in a composite (e.g. a composite pieceor pieces are adhered, or attached), or may be coated in the compositeprecursor and then the composite is cured on the component. In anotherexample, an adhesive material may be interposed between two components.In yet another example, a composite may be formed into a piece havingappropriate dimensions for incorporation into a device or structure.

In some aspects, the disclosure relates to a composite, where inexamples the composite comprises one or more epoxidized oils and one ormore resin materials including carboxylic functionality. In someexamples, the one or more epoxidized oils comprise linseed oil,vegetable oil, soybean oil, or a combination thereof. In certainembodiments, the one or more epoxidized oils are derived from one ormore plant based raw materials. In various examples, the one or moreresin materials comprise an acrylic resin, a polyester resin, or acombination thereof. In certain embodiments, the composite furthercomprises one or more fillers. In various examples, the one or morefillers comprise quartz granules, marble granules, or a combinationthereof. In some embodiments, the fillers have a size range of 0.2-500μm.

In various examples of these aspects, the one or more oils and one ormore resin materials are cured into a hard, durable composite. In someembodiments, the one or more resin materials have molecular weight ofabout 600-15,000 Daltons. In certain examples, the one or moreepoxidized oils are between 10-70% of the composite, by weight, between10-50% of the composite, by weight, between 15-45% of the composite, byweight, and/or between 35-45% of the composite, by weight (or theseamounts may be the relative weight of the epoxy and resin components,where additional fillers/additives are also present, when used), orabout 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about35%, or about 40% or more. In certain examples, the composite has aBarcol Hardness of 70 BU-80 BU, a Barcol Hardness of 70 BU or more,about 75 or more, or a Barcol Hardness of 80 BU or more. In someexamples, the composite further comprises one or more UV stabilizers,one or more thixotropic binders, one or more processing aids, or acombination thereof. In certain examples, the one or more processingaids comprise one or more solvents, or optionally, the processing aid isused during in a step of forming the composite, but is then removed ordried off prior to curing the components into a composite.

In other aspects, the disclosure relates to process, in examples aprocess comprising heating one or more epoxidized oils, one or moreresin materials including carboxylic functionality above the glasstransition temperature of the one or more resin materials and mixing theheated one or more oils and one or more materials to form a mixture, andcuring the mixture to form a composite. In some examples, one or morefillers are heated and mixed with the one or more oils and one or morematerials. In certain examples, one or more solvents are heated andmixed with the one or more oils and one or more materials.

These materials, compositions, formulations, systems and processdescriptions are merely examples. In certain embodiments, the materials,compositions, formulations, systems include additional combinationsand/or substitutions of some or all of the features, materials, and/orcomponents described above. Moreover, additional and alternativesuitable variations, forms and components for the materials,compositions, formulations, and systems will be recognized by thoseskilled in the art given the benefit of this disclosure. Any of thefeatures or materials described herein regarding materials,compositions, composites, formulations, or systems (such as but notlimited to devices or components partially or entirely coated in one ofthe above compositions), may be utilized or incorporated into othermaterials, compositions, composites, formulations, or systems. Forexample, materials and/or properties described in reference to acomposite may be utilized or present in an adhesive.

This disclosure also merely provides examples of the processes and/orprocess steps that may be performed in one or more embodiments, andadditional and alternative suitable variations, steps, and combinationsof steps will be recognized by those skilled in the art given thebenefit of this disclosure. Finally, any of the features discussed inthe example embodiments of the processes may be features of embodimentsof the materials, compositions, formulations, systems (or componentsthereof), and vice versa. Moreover, steps, and combinations of stepsdescribe din certain example embodiments may be added to or combinedwith other example steps and/or processes described with respect toother embodiments.

What is claimed is:
 1. A process comprising: mixing a liquid reactivediluent with one or more filler materials to provide coated surfaces ofthe one or more filler materials; mixing the coated one or more fillermaterials with a reactive thermoplastic powdered resin, wherein aparticle size of the reactive thermoplastic powdered resin in smallerthan a particle size of at least one of the filler materials; softeningor melting the reactive thermoplastic powdered resin so that the resinmaterial diffuses and further mixes with the liquid reactive diluent toprovide a diffused mixture; and compacting and curing the diffusedmixture to provide a thermoset composite material.
 2. The process ofclaim 1, wherein the liquid reactive diluent comprises an epoxy resin,an amino resin, or both an epoxy resin and an amino resin, and whereinthe thermoplastic powdered resin comprises an acrylic resin, a polyesterresin, an epoxy resin, a solid anhydride compound, or a polyacidcompound.
 3. The process of claim 1, wherein the liquid reactive diluentcomprises an amino resin, and wherein the powdered resin comprises ahydroxyl functional polyester or a hydroxyl functional acrylate.
 4. Theprocess of claim 1, wherein the liquid reactive diluent is amultifunctional acrylate or a vinyl compound and the powdered resin isan unsaturated polyester or acrylic resin and wherein the composition iscured by a thermally initiated curing process using a peroxideinitiator.
 5. The process of claim 1, wherein the liquid reactivediluent is a polyisocyanate, and wherein the powdered resin includes oneor more of a hydroxyl functional polyester, a hydroxyl functionalacrylic, or a polyether polyol.
 6. The process of claim 1, wherein theliquid reactive diluent is a vegetable oil based epoxy with epoxyequivalent weight of 150 to 250, and wherein the powdered resin is acarboxyl functional polyester or acrylic with acid value of 50 to 350.7. The process of claim 1, wherein the powdered resin is doped with anamount of the liquid reactive diluent without agglomerating ortackifying the powder.
 8. The process of claim 1, wherein the liquidreactive diluent is doped with an additional liquid reactive componentthat comprises one or more of the functional groups that are present inthe powdered resin.
 9. The process of claim 1, further comprising addinga wetting agent, an adhesion promotor, or both a wetting agent and anadhesion promotor to the liquid reactive diluent.
 10. The process ofclaim 1, further comprising mixing powdered resin material with fineamorphous silica with a size of less than 0.05 microns.
 11. The processof claim 1, wherein the particle size of the powdered resin is under 500microns.
 12. The process of claim 1, wherein the powdered resin ismelted by heat to provide the diffused mixture prior to compaction. 13.The process of claim 1, wherein the powdered resin is softened by heatto provide the diffused mixture prior to compaction.
 14. The process ofclaim 1, wherein the diffused mixture is subjected to a vacuum, anon-ambient pressure, vibration, heat, or a combination thereof, duringthe compacting.
 15. The process of claim 1, wherein the mixture is curedin a three-dimensional enclosed mold.
 16. The process of claim 1,wherein a catalyst is added to the liquid reactive diluent, one or morefiller materials, and powdered resin mixture prior to the softening ormelting, or is incorporated in the powdered resin.
 17. A thermosetcomposite material comprising a first liquid resin component and asecond thermoplastic powdered resin component that were reacted andcured to provide a cross-linked matrix, and one or more filler materialsdispersed within the matrix, wherein a particle size of the reactivethermoplastic powdered resin is smaller than a particle size of at leastone of the filler materials, and wherein the thermoset compositematerial is substantially free of voids.
 18. The composite material ofclaim 17, wherein the first liquid resin component comprises an epoxyresin, an amino resin, or both an epoxy resin and an amino resin, andwherein the thermoplastic powdered resin comprises an acrylic resin, apolyester resin, an epoxy resin, a solid anhydride compound, or apolyacid compound.
 19. The composite material of claim 17, wherein theone or more filler materials comprise quartz granules, marble granules,carbon fibers, carbon tubes, chopped glass or glass fibers, fabric,silica, ceramic, or a combination thereof.
 20. The composite material ofclaim 17, wherein the equivalent ratio of the first and second resincomponents is between 0.5 to 1.5.
 21. The process of claim 1, wherein anaverage molecular weight of the liquid reactive diluent is greater than150 Daltons and less than 5000 Daltons, and wherein an average molecularweight of the reactive thermoplastic powdered resin greater than 100Daltons and less than 25,000 Daltons.
 22. The process of claim 1,wherein a reactive solid is dissolved in the liquid reactive diluent ata temperature under 100° C., and wherein the liquid with the dissolvedsolids wets and coats the surfaces of the one or more fillers.